Materials and methods for stress reduction in semiconductor wafer passivation layers

ABSTRACT

The present invention provides polyimide polymer materials for passivating semiconductor wafers and methods for fabricating thereof. The present invention further provides a device that includes a semiconductor wafer and a passivating layer disposed on the surface of the wafer, wherein the passivating layer comprises such polyimide polymers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is claims the benefit of priority under 35 USC §119 ofU.S. Provisional Application Ser. No. 61/239,758 filed Sep. 3, 2009, theentire disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates generally to passivating layers forsilicon wafers. More particularly, the invention relates to compositionscontaining low modulus photoimagable polyimides for use as passivatinglayers.

BACKGROUND OF THE INVENTION

Polyimides exhibit an attractive combination of thermal stability (>500°C.), mechanical toughness and chemical resistance, in addition to havingexcellent dielectric properties. Because of their high degree ofductility and inherently low CTE, polyimides can be readily implementedinto a variety of microelectronic applications.

Polyimide films are frequently used as passivation layers for siliconwafers. Polyimide passivation layers are typically 4-6 microns inthickness, and protect the delicate thin films of metal and oxides onthe chip surface from damage during handling and from induced stressafter encapsulation in plastic molding compound. Patterning is simpleand straightforward. Because of the low defect density and robust plasmaetch resistance inherent with polyimide films, a “single mask” processcan be implemented, which permits the polyimide layer to function bothas a stress buffer and as a dry etch mask for an underlying siliconnitride layer. In addition, polyimide layers have been readily used forflip chip bonding applications, including both C-4 and dual-layer bondpad redistribution (BPR) applications. Polyimide layers can be patternedto form the structural components in microelectromechanical systems(MEMS).

Polyimides may also serve as an interlayer dielectric in bothsemiconductors and thin film multichip modules (MCM-D's). The lowdielectric constant, low stress, high modulus, and inherent ductility ofpolyimide films make them well suited for these multiple layerapplications. Other uses for polyimides include alignment and/ordielectric layers for displays, and as a structural layer inmicromachining applications. In lithium-ion battery technology,polyimide films can be used as protective layers for PTC thermistor(positive temperature coefficient) controllers.

In the fabrication of microelectronic devices, polyimides are typicallyapplied as a solution of the corresponding polyamic acid precursors ontoa substrate, and then thermally cured into a smooth, rigid, intractablepolymeric film or structural layer. The film can be patterned using alithographic (photographic) process in conjunction with liquidphotoresists. Typically, polyimides are formed in situ throughcyclodehydration of the polyamic acid precursors. This imidization stepalso requires the evaporation of high boiling, polar aprotic solvents,which can be difficult to drive away as the polyimide is formed.

Existing polyimide passivation materials generate a high degree ofstress on the wafer. This stress is known to cause delamination of thepassivation material. Moreover, as silicon wafers have become thinner,it has been found that the polyimides used for passivation layers tendto warp the wafer upon thermal cure, resulting in a concave or convexwafer surface. This phenomenon creates a variety of problems for thesemiconductor fabrication and packaging industry.

Conventional polyimide passivation materials are generally hydrophilicand usually require tedious multi-step processes to form the viasrequired for electrical interconnects. For example, polyimide materialshave been used as interlayer dielectric materials in microelectronicdevices such as integrated circuits (IC's) due to their having adielectric constant that is lower than that of silicon dioxide. Also,such polyimide materials can serve as a planarization layer for IC's asthey are generally applied in a liquid form, allowed to level, andsubsequently cured. However, polyimide materials readily absorb moistureeven after curing and this absorption can result in device failure. Inaddition, polyimides are generally not easily patterned as is oftenrequired in the manufacture of IC's and other microelectronic devices.

Accordingly, there is a need for hydrophobic, low modulus polyimidesthat are compatible with very thin silicon wafers, i.e., polyimidepassivation layers that will not warp thin silicon wafers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1-4 show films coated with passivation layers of the inventionprepared with imide-extended BMI compounds that have been photoimagedwith UV light and developed with toluene. The circular holes correspondto opaque areas (therefore un-cured, soluble regions of the film) in themask that was used to pattern the film and the continuous film in whichthe holes are embedded correspond to transparent areas of the mask(therefore cured, insoluble regions of the film) used to pattern thefilm.

FIG. 1 shows a developed photoimaged film in which the mask had 8 mildiameter opaque dots with 20 mil center-to-center spacing (8 mil dots,20 mil spacing).

FIG. 2 shows a developed film that has 4.6 mil holes and 9.5 mil spacingbetween holes (5 mil dots, 10 mil spacing).

FIG. 3 shows a developed film with 3.4 mil holes and 10 mil spacing (3mil dots, 100 mil spacing).

FIG. 4 shows schematically a semiconductor wafer and a passivating layerdisposed on the surface of the wafer, having various wafer/passivatinglayer combinations.

SUMMARY OF THE INVENTION

According to embodiments of the invention, a device is provided,comprising a semiconductor wafer and a passivating layer disposed on thesurface of the wafer. According to some embodiments, the passivatinglayer is comprised of a polyimide polymer having the molecular weightfraction of the combined contents of nitrogen and oxygen that is lessthan about 20%, such as imide-extended bismaleimides, or graftpolymaleimides described in U.S. Pat. No. 7,208,566, the contents ofwhich is incorporated herein by reference in its entirety.

According to some embodiments, a suitable polyimide polymer having themolecular weight fraction of the combined contents of nitrogen andoxygen that is less than about 20%, may be a polyimide comprising astructure selected from the group consisting of structures I, II andIII:

wherein each of R, R₃ and Q is independently selected from the groupconsisting of substituted or unsubstituted aliphatic, alkenyl, aromatic,heteroaromatic and siloxane moieties, R₂ in each structure I, II and IIIis independently selected from the group consisting of H or methyl, R₄is selected from the group consisting of substituted or unsubstitutedlinear, branched, cyclic aliphatic or alkenyl moieties having between 2and about 500 carbon atoms, and substituted or unsubstituted aromaticmoieties, n is an integer having the value between 1 to about 10, andthe symbol “

” depicts schematically a macromolecular chain to which the structure IIor III is covalently attached.

DETAILED DESCRIPTION

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention claimed. As used herein, theuse of the singular includes the plural unless specifically statedotherwise. As used herein, “or” means “and/or” unless stated otherwise.Furthermore, use of the term “including” as well as other forms, such as“includes,” and “included,” is not limiting. The section headings usedherein are for organizational purposes only and are not to be construedas limiting the subject matter described.

Unless specific definitions are provided, the nomenclatures utilized inconnection with, and the laboratory procedures and techniques ofanalytical chemistry, synthetic organic and inorganic chemistrydescribed herein are those known in the art, such as those set forth in“IUPAC Compendium of Chemical Terminology: IUPAC Recommendations (TheGold Book)” (McNaught ed.; International Union of Pure and AppliedChemistry, 2^(nd) Ed., 1997) and “Compendium of Polymer Terminology andNomenclature: IUPAC Recommendations 2008” (Jones et al., eds;International Union of Pure and Applied Chemistry, 2009). Standardchemical symbols are used interchangeably with the full namesrepresented by such symbols. Thus, for example, the terms “hydrogen” and“H” are understood to have identical meaning. Standard techniques may beused for chemical syntheses, chemical analyses, and formulation.

Definitions

“About” as used herein means that a number referred to as “about”comprises the recited number plus or minus 1-10% of that recited number.For example, “about” 100 degrees can mean 95-105 degrees or as few as99-101 degrees depending on the situation. Whenever it appears herein, anumerical range such as “1 to 20” refers to each integer in the givenrange; e.g., “1 to 20 carbon atoms” means that an alkyl group cancontain only 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up toand including 20 carbon atoms (although the term “alkyl” also includesinstances where no numerical range of carbon atoms is designated).

“Passivation” as used herein, refers to the process of making a material“passive” in relation to another material or condition. “Passivationlayers” are commonly used to encapsulate semiconductor devices, such assemiconductor wafers, to isolate the device from its immediateenvironment and, thereby, to protect the device from oxygen, water,etc., as well airborne or space-borne contaminants, particulates,humidity and the like. Passivation layers are typically formed frominert materials that are used to coat the device. This encapsulationprocess also passivates semiconductor devices by terminating danglingbonds created during manufacturing processes and by adjusting thesurface potential to either reduce or increase the surface leakagecurrent associated with these devices.

In certain embodiments of the invention, passivation layers (PL) containdielectric material that is disposed over a microelectronic device. SuchPLs are typically patterned to form openings therein that provide formaking electrical contact to the microelectronic device. Often apassivation layer is the last dielectric material disposed over a deviceand serves as a protective layer.

“Interlayer Dielectric Layer” (ILD) refers to a layer of dielectricmaterial disposed over a first pattern of conductive traces and betweensuch first pattern and a second pattern of conductive traces. Such ILDlayer is typically patterned to form openings therein (generallyreferred to as “vias”) to provide for electrical contact between thefirst and second patterns of conductive traces in specific regions.Other regions of such ILD layer are devoid of vias and thus preventelectrical contact between the conductive traces of the first and secondpatterns in such other regions.

“Coating composition” as used herein, refers to un-cured mixtures inwhich the individual components in the mixture retain the chemical andphysical characteristics of the original individual components of whichthe mixture is made. Coating compositions are typically malleable andmay be liquids, solutions of thermosetting resins, neat thermoplasticsolids or another form that can be applied to an item so that it cancoat another item.

“Cured coating,” “cured film composition” or “cured compound” refers toresin components and mixtures obtained from reactive curable originalcompound(s) or mixture(s) thereof which have undergone a chemical and/orphysical changes such that the original compound(s) or mixture(s)is(are) transformed into a solid, substantially non-flowing material. Atypical curing process may involve crosslinking.

“Curable” means that an original compound(s) or composition material(s)can be transformed into a solid, substantially non-flowing material bymeans of chemical reaction, crosslinking, radiation crosslinking, or thelike. Thus, compositions of the invention are curable, but unlessotherwise specified, the original compound(s) or composition material(s)is(are) not cured.

“Photoimageable”, as used herein, refers to the ability of a compound orcomposition to be selectively cured only in areas exposed to light. Theexposed areas of the compound are thereby rendered cured and insoluble,while the unexposed area of the compound or composition remain un-curedand therefore soluble in a developer solvent. Typically, this operationis conducted using ultraviolet light as the light source and a photomaskas the means to define where the exposure occurs. The selectivepatterning of dielectric layers on a silicon wafer can be carried out inaccordance with various photolithographic techniques known in the art.In one method, a photosensitive polymer film is applied over the desiredsubstrate surface and dried. A photomask containing the desiredpatterning information is then placed in close proximity to thephotoresist film. The photoresist is irradiated through the overlyingphotomask by one of several types of imaging radiation including UVlight, e-beam electrons, x-rays, or ion beam. Upon exposure to theradiation, the polymer film undergoes a chemical change (crosslinks)with concomitant changes in solubility. After irradiation, the substrateis soaked in a developer solution that selectively removes thenon-crosslinked or unexposed areas of the film.

“Thermoplastic,” as used herein, refers to the ability of a compound,composition or other material (e.g. a plastic) to dissolve in a suitablesolvent or to melt to a liquid when heated and freeze to a solid, oftenbrittle and glassy, state when cooled sufficiently.

“Thermoset,” as used herein, refers to the ability of a compound,composition or other material to irreversibly “cure” resulting in asingle tridimensional network that has greater strength and lesssolubility compared to the non-cured product. Thermoset materials aretypically polymers that may be cured, for example, through heat (e.g.above 200° Celsius), via a chemical reaction (e.g. epoxy ring-opening,free-radical polymerization, etc.), or through irradiation (e.g. visiblelight, U.V. light, electron beam radiation, ion-beam radiation, or X-rayirradiation).

Thermoset materials, such as thermoset polymers or resins, are typicallyliquid or malleable forms prior to curing, and therefore may be moldedor shaped into their final form, and/or used as adhesives. Curingtransforms the thermoset resin into a rigid infusible and insolublesolid or rubber by a cross-linking process. Thus, energy and/orcatalysts are typically added that cause the molecular chains to reactat chemically active sites (unsaturated or epoxy sites, for example),linking the polymer chains into a rigid, 3-D structure. Thecross-linking process forms molecules with a higher molecular weight andresultant higher melting point. During the reaction, when the molecularweight of the polymer has increased to a point such that the meltingpoint is higher than the surrounding ambient temperature, the polymerbecomes a solid material.

“Cross-linking,” as used herein, refers to the attachment of two or moreoligomer or longer polymer chains by bridges of an element, a moleculargroup, a compound, or another oligomer or polymer. Crosslinking may takeplace upon heating or exposure to light; some crosslinking processes mayalso occur at room temperature or a lower temperature. As cross-linkingdensity is increased, the properties of a material can be changed fromthermoplastic to thermosetting.

A “die” or “semiconductor die” as used herein, refers to a small blockof semiconducting material, on which a functional circuit is fabricated.

A “flip-chip” semiconductor device is one in which a semiconductor dieis directly mounted to a wiring substrate, such as a ceramic or anorganic printed circuit board. Conductive terminals on the semiconductordie, usually in the form of solder bumps, are directly physically andelectrically connected to the wiring pattern on the substrate withoutuse of wire bonds, tape-automated bonding (TAB), or the like. Becausethe conductive solder bumps making connections to the substrate are onthe active surface of the die or chip, the die is mounted in a face-downmanner, thus the name “flip-chip.”

“Underfill,” “underfill composition” and “underfill material” are usedinterchangeably to refer to a material, typically polymericcompositions, used to fill gaps between a semiconductor component, suchas a semiconductor die, and a substrate. “Underfilling” refers to theprocess of applying an underfill composition to a semiconductorcomponent-substrate interface, thereby filling the gaps between thecomponent and the substrate.

The term “monomer” refers to a molecule that can undergo polymerizationor copolymerization thereby contributing constitutional units to theessential structure of a macromolecule (a polymer).

“Polymer” and “polymer compound” are used interchangeably herein, torefer generally to the combined products of a single chemicalpolymerization reaction. Polymers are produced by combining monomersubunits into a covalently bonded chain. Polymers that contain only asingle type of monomer are known as “homopolymers,” while polymerscontaining a mixture of monomers are known as “copolymers.”

The term “copolymers” is inclusive of products that are obtained bycopolymerization of two monomer species, those obtained from threemonomers species (terpolymers), those obtained from four monomersspecies (quaterpolymers), etc. It is well known in the art thatcopolymers synthesized by chemical methods include, but are not limitedto, molecules with the following types of monomer arrangements:

alternating copolymers, which contain regularly alternating monomerresidues;

periodic copolymers, which have monomer residue types arranged in arepeating sequence;

random copolymers, which have a random sequence of monomer residuetypes;

statistical copolymers, which have monomer residues arranged accordingto a known statistical rule; and

block copolymers, which have two or more homopolymer subunits linked bycovalent bonds. The blocks of homopolymer within block copolymers, forexample, can be of any length and can be blocks of uniform or variablelength. Block copolymers with two or three distinct blocks are calleddiblock copolymers and triblock copolymers, respectively; and

star copolymers, which have chains of monomer residues having differentconstitutional or configurational features that are linked through acentral moiety.

The skilled artisan will appreciate that a single copolymer molecule mayhave different regions along its length that can be characterized as analternating, periodic, random, etc. A copolymer product of a chemicalpolymerization reaction may contain individual polymeric fragments thateach differ in the arrangement of monomer units. The skilled artisanwill further be knowledgeable in methods for synthesizing each of thesetypes of copolymers, and for varying reaction conditions to favor onetype over another.

Furthermore, the length of a polymer chain according to the presentinvention, will typically vary over a range or average size produced bya particular reaction. The skilled artisan will be aware, for example,of methods for controlling the average length of a polymer chainproduced in a given reaction and also of methods for size-selectingpolymers after they have been synthesized.

Unless a more restrictive term is used, polymer is intended to encompasshomopolymers, and copolymers having any arrangement of monomer subunitsas well as copolymers containing individual molecules having more thanone arrangement. With respect to length, unless otherwise indicated, anylength limitations recited for the polymers described herein are to beconsidered averages of the lengths of the individual molecules inpolymer.

“Thermoplastic elastomer” or “TPE”, as used herein refers to a class ofcopolymers that consist of materials with both thermoplastic andelastomeric properties.

“Hard blocks” or “hard segments” as used herein refer to a block of acopolymer (typically a thermoplastic elastomer) that is hard at roomtemperature by virtue of a high melting point (Tm) or T_(g). Bycontrast, “soft blocks” or “soft segments” have a T_(g) below roomtemperature.

As used herein, “oligomer” or “oligomeric” refers to a polymer having afinite and moderate number of repeating monomers structural units.Oligomers of the invention typically have 2 to about 100 repeatingmonomer units; frequently 2 to about 30 repeating monomer units; andoften 2 to about 10 repeating monomer units; and usually have amolecular weight up to about 3,000.

The skilled artisan will appreciate that oligomers and polymers may,depending on the availability of polymerizable groups or side chains,subsequently be incorporated as monomers in further polymerization orcrosslinking reactions.

As used herein, “aliphatic” refers to any alkyl, alkenyl, cycloalkyl, orcycloalkenyl moiety.

“Aromatic hydrocarbon” or “aromatic” as used herein, refers to compoundshaving one or more benzene rings.

“Alkane,” as used herein, refers to saturated straight-chain, branchedor cyclic hydrocarbons having only single bonds. Alkanes have generalformula C_(n)H_(2n+2). “Cycloalkane,” refers to an alkane having one ormore rings in its structure.

As used herein, “alkyl” refers to straight or branched chain hydrocarbylgroups having from 1 up to about 500 carbon atoms. “Lower alkyl” refersgenerally to alkyl groups having 1 to 6 carbon atoms. The terms “alkyl”and “substituted alkyl” include, respectively, substituted andunsubstituted C₁-C₅₀₀ straight chain saturated aliphatic hydrocarbongroups, substituted and unsubstituted C₂-C₂₀₀ straight chain unsaturatedaliphatic hydrocarbon groups, substituted and unsubstituted C₄-C₁₀₀branched saturated aliphatic hydrocarbon groups, substituted andunsubstituted C₁-C₅₀₀ branched unsaturated aliphatic hydrocarbon groups.

For example, the definition of “alkyl” includes but is not limited to:methyl (Me), ethyl (Et), propyl (Pr), butyl (Bu), pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, ethenyl, propenyl, butenyl, penentyl,hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, isopropyl(i-Pr), isobutyl (i-Bu), tert-butyl (t-Bu), sec-butyl (s-Bu), isopentyl,neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclopentenyl, cyclohexenyl, cycloheptenyl,cyclooctenyl, methylcyclopropyl, ethylcyclohexenyl, butenylcyclopentyl,tricyclodecyl, adamantyl, norbornyl and the like.

“Substituted alkyl” refers to alkyl moieties bearing substituents thatinclude but are not limited to alkyl, alkenyl, alkynyl, hydroxy, oxo,alkoxy, mercapto, cycloalkyl, substituted cycloalkyl, heterocyclic,substituted heterocyclic, aryl, substituted aryl (e.g., arylC₁₋₁₀alkylor arylC₁₋₁₀alkyloxy), heteroaryl, substituted heteroaryl (e.g.,heteroarylC₁₋₁₀alkyl), aryloxy, substituted aryloxy, halogen, haloalkyl(e.g., trihalomethyl), cyano, nitro, nitrone, amino, amido, carbamoyl,═O, ═CH—, —C(O)H, —C(O)O—, —C(O)—, —S—, —S(O)₂—, —OC(O)—O—, —NR—C(O)—,—NR—C(O)—NR—, —OC(O)—NR—, where R is H or lower alkyl, acyl, oxyacyl,carboxyl, carbamate, sulfonyl, sulfonamide, sulfuryl, C₁₋₁₀alkylthio,arylC₁₋₁₀alkylthio, C₁₋₁₀alkylamino, arylC₁₋₁₀alkylamino,N-aryl-N—C₁₋₁₀alkylamino, C₁₋₁₀alkyl carbonyl, arylC₁₋₁₀alkylcarbonyl,C₁₋₁₀alkylcarboxy, aryl C₁₋₁₀alkylcarboxy, C₁₋₁₀alkyl carbonylamino,aryl C₁₋₁₀alkylcarbonylamino, tetrahydrofuryl, morpholinyl, piperazinyl,and hydroxypyronyl.

As used herein, “cycloalkyl” refers to cyclic ring-containing groupscontaining in the range of about 3 up to about 20 carbon atoms,typically 3 to about 15 carbon atoms. In certain embodiments, cycloalkylgroups have in the range of about 4 up to about 12 carbon atoms, and inyet further embodiments, cycloalkyl groups have in the range of about 5up to about 8 carbon atoms. and “substituted cycloalkyl” refers tocycloalkyl groups further bearing one or more substituents as set forthbelow.

As used herein, the term “aryl” represents an unsubstituted, mono-, di-or trisubstituted monocyclic, polycyclic, biaryl aromatic groupscovalently attached at any ring position capable of forming a stablecovalent bond, certain preferred points of attachment being apparent tothose skilled in the art (e.g., 3-phenyl, 4-naphtyl and the like). Thearyl substituents are independently selected from the group consistingof halo, —OH, —SH, —CN, —NO₂, trihalomethyl, hydroxypyronyl, C₁₋₁₀alkyl,arylC₁₋₁₀alkyl, C₁₋₁₀alkyloxyC₁₋₁₀alkyl, arylC₁₋₁₀alkyloxyC₁₋₁₀alkyl,C₁₋₁₀alkylthioC₁₋₁₀alkyl, arylC₁₋₁₀alkylthioC₁₋₁₀alkyl,C₁₋₁₀alkylaminoC₁₋₁₀alkyl, arylC₁₋₁₀alkylaminoC₁₋₁₀alkyl,N-aryl-N-C₁₋₁₀alkylaminoC₁₋₁₀alkyl, C₁₋₁₀alkylcarbonylC₁₋₁₀alkyl, arylC₁₋₁₀alkylcarbonyl C₁₋₁₀alkyl, C₁₋₁₀alkylcarboxyC₁₋₁₀alkyl,arylC₁₋₁₀alkylcarboxyC₁₋₁₀alkyl, C₁₋₁₀alkylcarbonylaminoC₁₋₁₀alkyl, andarylC₁₋₁₀alkylcarbonylaminoC₁₋₁₀alkyl.

Some specific examples of moieties encompassed by the definition of“aryl” include but are not limited to phenyl, biphenyl, naphthyl,dihydronaphthyl, tetrahydronaphthyl, indenyl, indanyl, azulenyl,anthryl, phenanthryl, fluorenyl, pyrenyl and the like. “Substitutedaryl” refers to aryl groups further bearing one or more substituents asset forth below.

As used herein, “arylene” refers to a divalent aryl moiety. “Substitutedarylene” refers to arylene moieties bearing one or more substituents asset forth above.

As used herein, “alkylaryl” refers to alkyl-substituted aryl groups and“substituted alkylaryl” refers to alkylaryl groups further bearing oneor more substituents as set forth below.

As used herein, “arylalkyl” refers to aryl-substituted alkyl groups and“substituted arylalkyl” refers to arylalkyl groups further bearing oneor more substituents as set forth below. Some examples of included butare not limited to (4-hydroxyphenyl)ethyl, or (2-aminonaphthyl)hexenyl.

As used herein, “arylalkenyl” refers to aryl-substituted alkenyl groupsand “substituted arylalkenyl” refers to arylalkenyl groups furtherbearing one or more substituents as set forth below.

As used herein, “arylalkynyl” refers to aryl-substituted alkynyl groupsand “substituted arylalkynyl” refers to arylalkynyl groups furtherbearing one or more substituents as set forth below.

As used herein, “aroyl” refers to aryl-carbonyl species such as benzoyland “substituted aroyl” refers to aroyl groups further bearing one ormore substituents as set forth below.

As used herein, “hetero” refers to groups or moieties containing one ormore heteroatoms such as N, O, Si and S. Thus, for example“heterocyclic” refers to cyclic (i.e., ring-containing) groups havinge.g. N, O, Si or S as part of the ring structure, and having in therange of 3 up to 14 carbon atoms. “Heteroaryl” and “heteroalkyl”moieties are aryl and alkyl groups, respectively, containing e.g. N, O,Si or S as part of their structure. The terms “heteroaryl”,“heterocycle” or “heterocyclic” refer to a monovalent unsaturated grouphaving a single ring or multiple condensed rings, from 1 to 8 carbonatoms and from 1 to 4 hetero atoms selected from nitrogen, sulfur oroxygen within the ring.

The definition of heteroaryl includes but is not limited to thienyl,benzothienyl, isobenzothienyl, 2,3-dihydrobenzothienyl, furyl, pyranyl,benzofuranyl, isobenzofuranyl, 2,3-dihydrobenzofuranyl, pyrrolyl,pyrrolyl-2,5-dione, 3-pyrrolinyl, indolyl, isoindolyl, 3H-indolyl,indolinyl, indolizinyl, indazolyl, phthalimidyl (orisoindoly-1,3-dione), imidazolyl. 2H-imidazolinyl, benzimidazolyl,pyridyl, pyrazinyl, pyradazinyl, pyrimidinyl, triazinyl, quinolyl,isoquinolyl, 4H-quinolizinyl, cinnolinyl, phthalazinyl, quinazolinyl,quinoxalinyl, 1,8-naphthyridinyl, pteridinyl, carbazolyl, acridinyl,phenazinyl, phenothiazinyl, phenoxazinyl, chromanyl, benzodioxolyl,piperonyl, purinyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl,isothiazolyl, benzthiazolyl, oxazolyl, isoxazolyl, benzoxazolyl,oxadiazolyl, thiadiazolyl, pyrrolidinyl-2,5-dione,imidazolidinyl-2,4-dione, 2-thioxo-imidazolidinyl-4-one,imidazolidinyl-2,4-dithione, thiazolidinyl-2,4-dione,4-thioxo-thiazolidinyl-2-one, piperazinyl-2,5-dione,tetrahydro-pyridazinyl-3,6-dione,1,2-dihydro-[1,2,4,5]tetrazinyl-3,6-dione,[1,2,4,5]tetrazinanyl-3,6-dione, dihydro-pyrimidinyl-2,4-dione,pyrimidinyl-2,4,6-trione, 1H-pyrimidinyl-2,4-dione,5-iodo-1H-pyrimidinyl-2,4-dione, 5-chloro-1H-pyrimidinyl-2,4-dione,5-methyl-1H-pyrimidinyl-2,4-dione, 5-isopropyl-1H-pyrimidinyl-2,4-dione,5-propynyl-1H-pyrimidinyl-2,4-dione,5-trifluoromethyl-1H-pyrimidinyl-2,4-dione, 6-amino-9H-purinyl,2-amino-9H-purinyl, 4-amino-1H-pyrimidinyl-2-one,4-amino-5-fluoro-1H-pyrimidinyl-2-one,4-amino-5-methyl-1H-pyrimidinyl-2-one,2-amino-1,9-dihydro-purinyl-6-one, 1,9-dihydro-purinyl-6-one,1H-[1,2,4]triazolyl-3-carboxylic acid amide,2,6-diamino-N.sub.6-cyclopropyl-9H-purinyl,2-amino-6-(4-methoxyphenylsulfanyl)-9H-purinyl,5,6-dichloro-1H-benzoimidazolyl,2-isopropylamino-5,6-dichloro-1H-benzoimidazolyl,2-bromo-5,6-dichloro-1H-benzoimidazolyl, and the like. Furthermore, theterm “saturated heterocyclic” represents an unsubstituted, mono-, di- ortrisubstituted monocyclic, polycyclic saturated heterocyclic groupcovalently attached at any ring position capable of forming a stablecovalent bond, certain preferred points of attachment being apparent tothose skilled in the art (e.g., 1-piperidinyl, 4-piperazinyl and thelike).

Hetero-containing groups may also be substituted. For example,“substituted heterocyclic” refers to a ring-containing group having inthe range of 3 up to 14 carbon atoms that contains one or moreheteroatoms and also bears one or more substituents, as set forth above.Examples of substituents include, but are not limited to halo, —OH, —SH,—CN, —NO₂, trihalomethyl, hydroxypyronyl, C₁₋₁₀alkyl, arylC₁₋₁₀alkyl,C₁₋₁₀alkyloxyC₁₋₁₀alkyl, arylC₁₋₁₀alkyloxy C₁₋₁₀alkyl,C₁₋₁₀-alkylthioC₁₋₁₀alkyl, arylC₁₋₁₀alkylthioC₁₋₁₀alkyl,C₁₋₁₀alkylaminoC₁₋₁₀alkyl, arylC₁₋₁₀alkylamino C₁₋₁₀alkyl,N-aryl-N-C₁₋₁₀alkylaminoC₁₋₁₀alkyl, C₁₋₁₀alkylcarbonylC₁₋₁₀alkyl,arylC₁₋₁₀alkylcarbonyl C₁₋₁₀alkyl, C₁₋₁₀alkylcarboxyC₁₋₁₀alkyl,arylC₁₋₁₀alkylcarboxyC₁₋₁₀alkyl C₁₋₁₀alkylcarbonylaminoC₁₋₁₀alkyl, andarylC₁₋₁₀alkylcarbonylamino C₁₋₁₀alkyl.

As used herein, “alkenyl,” “alkene” or “olefin” refers to straight orbranched chain unsaturated hydrocarbyl groups having at least onecarbon-carbon double bond, and having in the range of about 2 up to 500carbon atoms. In certain embodiments, alkenyl groups have in the rangeof about 5 up to about 250 carbon atoms, 5 up to about 100 carbon atoms,5 up to about 50 carbon atoms or 5 up to about 25 carbon atoms. In otherembodiments, alkenyl groups have in the range of about 6 up to about 500carbon atoms, 8 up to about 500 carbon atoms, 10 up to about 500 carbonatoms or 20 up to about 500 carbon atoms or 50 up to about 500 carbonatoms. In yet further embodiments, alkenyl groups have in the range ofabout 6 up to about 100 carbon atoms, 10 up to about 100 carbon atoms,20 up to about 100 carbon atoms or 50 up to about 100 carbon atoms,while in other embodiments, alkenyl groups have in the range of about 6up to about 50 carbon atoms, 6 up to about 25 carbon atoms, 10 up toabout 50 carbon atoms, or 10 up to about 25 carbon atoms. “Substitutedalkenyl” refers to alkenyl groups further bearing one or moresubstituents as set forth above.

As used herein, “alkylene” refers to a divalent alkyl moiety, and“oxyalkylene” refers to an alkylene moiety containing at least oneoxygen atom instead of a methylene (CH₂) unit. “Substituted alkylene”and “substituted oxyalkylene” refer to alkylene and oxyalkylene groupsfurther bearing one or more substituents as set forth above.

As used herein, “alkynyl” refers to straight or branched chainhydrocarbyl groups having at least one carbon-carbon triple bond, andhaving in the range of 2 up to about 100 carbon atoms, typically about 4to about 50 carbon atoms, and frequently about 8 to about 25 carbonatoms. “Substituted alkynyl” refers to alkynyl groups further bearingone or more substituents as set forth below.

As used herein, “arylene” refers to a divalent aryl moiety. “Substitutedarylene” refers to arylene moieties bearing one or more substituents asset forth above.

“Imide” as used herein, refers to a functional group having two carbonylgroups bound to a primary amine or ammonia. The general formula of animide is:

“Polyimides” are polymers of imide-containing monomers. Polyimides aretypically linear or cyclic. Non-limiting examples of linear and cyclic(e.g. an aromatic heterocyclic polyimide) polyimides are shown below forillustrative purposes.

“Maleimide,” as used herein, refers to an N-substituted maleimide havingthe formula as shown below:

-   -   where R is an aromatic, heteroaromatic, aliphatic, or polymeric        moiety.

“Bismaleimide” or “BMI”, as used herein, refers to compound in which twoimide moieties are linked by a bridge, i.e. a compound a polyimidehaving the general structure shown below:

where R is an aromatic, heteroaromatic, aliphatic, or polymeric moiety.BMIs can cure through an addition rather than a condensation reaction,thus avoiding problems resulting from the formation of volatiles. BMIscan be cured by a vinyl-type polymerization of a pre-polymer terminatedwith two maleimide groups.

As used herein, “maleate” refers to a compound bearing at least onemoiety having the structure:

As used herein, the terms “halogen,” “halide,” or “halo” includefluorine, chlorine, bromine, and iodine.

As used herein, “siloxane” refers to any compound containing a Si—Omoiety. Siloxanes may be either linear or cyclic. In certainembodiments, siloxanes of the invention include 2 or more repeatingunits of Si—O. Exemplary cyclic siloxanes includehexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and thelike.

The term “epoxy” also refers to thermosetting epoxide polymers that cureby polymerization and crosslinking when mixed with a catalyzing agent or“hardener,” also referred to as a “curing agent” or “curative.” Epoxiesof the present invention include, but are not limited to aliphatic,cycloaliphatic, glycidyl ether, glycidyl ester, glycidyl amine epoxies,and the like, and combinations thereof.

In addition, as used herein “C₃₆” refers to all possible structuralisomers of a 36 carbon aliphatic moiety, including branched isomers andcyclic isomers with up to three carbon-carbon double bonds in thebackbone. One non-limiting example of a moiety that the definition of“C₃₆” refers to is the moiety comprising a cyclohexane-based core andfour long “arms” attached to the core, as demonstrated by the followingstructure:

As used herein, a “primary amine terminated difunctional siloxanebridging group” refers to a moiety having the structural formula:

where each R is H or Me, each R′ is independently H, lower alkyl, oraryl; each of m and n is an integer having the value between 1 to about10, and q is an integer having the value between 1 and 100.

As used herein, the term “free radical initiator” refers to any chemicalspecies which, upon exposure to sufficient energy (e.g., light, heat, orthe like), decomposes into parts which are uncharged, but every one ofsuch part possesses at least one unpaired electron.

As used herein, the term “coupling agent” refers to chemical speciesthat are capable of bonding to a mineral surface and which also containpolymerizably reactive functional group(s) so as to enable interactionwith the adhesive composition. Coupling agents thus facilitate linkageof the die-attach paste to the substrate to which it is applied.

The term “solvent,” as used herein, refers to a liquid that dissolves asolid, liquid, or gaseous solute, resulting in a solution. “Co-solvent”refers to a second, third, etc. solvent used with a primary solvent.

As used herein, “polar protic solvents” are ones that contains an O—H orN—H bond, while “polar aprotic solvents” do not contain an O—H or N—Hbond.

“Glass transition temperature” or “T_(g)”: is used herein to refer tothe temperature at which an amorphous solid, such as a polymer, becomesbrittle on cooling, or soft on heating. More specifically, it defines apseudo second order phase transition in which a supercooled melt yields,on cooling, a glassy structure and properties similar to those ofcrystalline materials e.g. of an isotropic solid material.

“Modulus” or “Young's modulus” as used herein, is a measure of thestiffness of a material. Within the limits of elasticity, modulus is theratio of the linear stress to the linear strain which can be determinedfrom the slope of a stress-strain curve created during tensile testing.

The “Coefficient of Thermal Expansion” or “CTE” is a term of artdescribing a thermodynamic property of a substance. The CTE relates achange in temperature to the change in a material's linear dimensions.As used herein “α₁ CTE” or “α₁” refers to the CTE before the T_(g),while “α₂ CTE” refers to the CTE after the T_(g).

“Thixotropy” as used herein, refers to the property of a material whichenables it to stiffen or thicken in a relatively short time uponstanding, but upon agitation or manipulation to change to low-viscosityfluid; the longer the fluid undergoes shear stress, the lower itsviscosity. Thixotropic materials are therefore gel-like at rest butfluid when agitated and have high static shear strength and low dynamicshear strength, at the same time.

“Thermogravimetric analysis” or “TGA” refers to a method of testing andanalyzing a material to determine changes in weight of a sample that isbeing heated in relation to change in temperature. “Decomposition onset”refers to a temperature when the loss of weight in response to theincrease of the temperature indicates that the sample is beginning todegrade.

The term “Degree of Planarization” refers to the ability of the coatingmaterial to level or planarize the previously deposited layer with itsunderlying topography.

The parameter “molecular weight fraction of the combined contents ofnitrogen and oxygen” is calculated as follows: MFW=[(14×number of N inthe polyamide)+(16×number of O in the polyamide]/MWP, where MFW ismolecular weight fraction of the combined contents of nitrogen andoxygen, and MWP is the molecular weight of the polyamide.

Embodiments of the Invention

According to embodiments of the present invention, there are provideddevices comprising a semiconductor wafer and a passivating layerdisposed on the surface of the wafer. The passivating layer is comprisedof a polyimide polymer having the molecular weight fraction of thecombined contents of nitrogen and oxygen that is less than about 20%,such less than about 15%, for example, below about 12%. For comparison,the nitrogen plus oxygen molecular weight fraction of the traditionalpolyimide passivation coating materials is typically in the range of21-36%.

The polyimides that are utilized in the embodiments of the presentinvention to prepare the passivating layer are less subject to stresseffects than previously used polyimides; therefore, the polyimides usedin the present invention are compatible with very thin silicon wafers.The polyimides of this invention are fully imidized, and thus do notrequire further heat processing to cyclodehydrate amic acid residuesafter the passivation layer has been applied to a wafer. Polyimidessuitable for use in the methods and materials of the present inventioncan be supplied pre-dissolved in a relatively low boiling solvent (suchas solvents boiling at about 100° C.).

Another desirable feature of the polyimide compounds of this inventionis that they have much lower moisture uptake than the traditionalpolymidide passivation coatings. A further attractive feature ofinvention polyimides is that they are optionally photoimageable, therebyallowing for patterning of the passivation layer.

According to some embodiments, a suitable polyimide polymer (i.e., apolyimide having the molecular weight fraction of the combined contentsof nitrogen and oxygen that is less than about 20%), may be a polyimidecomprising a structure selected from the group consisting of structuresI, II and III:

where each of R, R₃ and Q is independently selected from the groupconsisting of substituted or unsubstituted aliphatic, alkenyl, aromatic,heteroaromatic and siloxane moieties, R₂ in each structure I, II and IIIis independently selected from the group consisting of H or methyl, R₄is selected from the group consisting of substituted or unsubstitutedlinear, branched, cyclic aliphatic or alkenyl moieties having between 2and about 500 carbon atoms, and substituted or unsubstituted aromaticmoieties, n is an integer having the value between 1 to about 10, andthe symbol “

” depicts schematically a macromolecular chain to which the structure IIor III is covalently attached.

For example, each of R, R₃ and Q in structures I or II can be anunsubstituted aromatic or heteroaromatic moiety having between 6 andabout 14 carbon atoms. In other embodiments, each of R, R₃ and Q each ofR, R₃ and Q in structures I or II can be a substituted or unsubstitutedsiloxane moiety having between 2 and about 50 silicon atoms. Such asiloxane moiety can be a polysiloxane, for example, a polysiloxanecomprising repeating units selected from dimethylsiloxane,methylphenylsiloxane, diphenylsiloxane or combinations thereof.

In some embodiments, in structures I-III, substituted aliphatic,aromatic, heteroaromatic, or siloxane moieties may comprise substituentsselected from an alkyl, an alkenyl, an alkynyl, hydroxyl, oxo, analkoxy, mercapto, a cycloalkyl, a substituted cycloalkyl, aheterocyclic, a substituted heterocyclic, an aryl, a substituted aryl, aheteroaryl, a substituted heteroaryl, an aryloxy, a substituted aryloxy,a halogen, a haloalkyl, cyano, nitro, nitrone, an amino, an amido,—C(O)H, —C(O)—, —C(O)—, —S—, —S(O)₂—, —OC(O)—O—, —NR—C(O)—,—NR—C(O)—NR—, and —OC(O)—NR—, wherein R can be any of H, a lower alkyl,an acyl, an oxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide orsulfuryl.

In certain embodiments, the polyimide polymer is an imide-extendedbismaleimide compounds having the structure:

wherein each of R and Q is independently a substituted or anunsubstituted aliphatic, alkenyl, aromatic, heteroaromatic, or siloxanemoiety; R₂ is H or methyl; and n is an integer having the value between1 and about 10, with the proviso that the imide-extended bismaleimide isnot

As used herein, the term “imide-extended” means that the compoundcontains at least one imide moiety in a non-terminal position of themolecule.

In another embodiment, the polyimide polymer is a compound having thestructure:

where R and Q are each independently substituted or unsubstitutedaliphatic, aromatic, heteroaromatic, siloxane, unsaturated hydrocarbon,polyester, polyamide, or polyurethane moieties; and X is a polymerizableor curative moiety.

In some embodiments, the polymerizable moiety is a cationicpolymerizable moiety, an anionic polymerizable moiety, a ring-openingpolymerizable moiety, or a free radical polymerizable moiety. In someembodiments, the polymerizable moiety is vinyl ether, vinyl ester,acrylate, methacrylate, epoxy, oxetane, oxazoline, benzoxazine,propargyl ether, urethane, norbornyl, maleimide, or nadimide. In someembodiments the curative is phenol, phenyl ester and the like.

Imide-extended bismaleimide compounds are readily prepared by atwo-step, single-pot synthesis as illustrated in are shown in U.S.Patent Publication No. 20110130485, FIG.1 (incorporated herein byreference). The first step involves the condensation of a dianhydridewith a dimer diamine to form an amine-terminated polyimide. The diamineshould be present in at least a slight excess of that necessary to formthe imide-linked diamine intermediate.

A wide variety of diamines are contemplated for use in the practice ofthe invention, such as for example, 1,10-diaminodecane;1,12-diaminododecane; dimer diamine; 1,2-diamino-2-methylpropane;1,2-diaminocyclohexane; 1,2-diaminopropane; 1,3-diaminopropane;1,4-diaminobutane; 1,5-diaminopentane; 1,7-diaminoheptane;1,8-diaminomenthane; 1,8-diaminooctane; 1,9-diaminononane;3,3′-diamino-N-methyldipropylamine; diaminomaleonitrile;1,3-diaminopentane; 9,10-diaminophenanthrene;4,4′-diaminooctafluorobiphenyl; 3,5-diaminobenzoic acid;3,7-diamino-2-methoxyfluorene; 4,4′-diaminobenzophenone;3,4-diaminobenzophenone; 3,4-diaminotoluene; 2,6-diaminoanthroquinone;2,6-diaminotoluene; 2,3-diaminotoluene; 1,8-diaminonaphthalene;2,4-diaminotoluene; 2,5-diaminotoluene; 1,4-diaminoanthroquinone;1,5-diaminoanthroquinone; 1,5-diaminonaphthalene;1,2-diaminoanthroquinone; 2,4-cumenediamine; 1,3-bisaminomethylbenzene;1,3-bisaminomethylcyclohexane; 2-chloro-1,4-diaminobenzene;1,4-diamino-2,5-dichlorobenzene; 1,4-diamino-2,5-dimethylbenzene;4,4′-diamino-2,2′-bistrifluoromethylbiphenyl;bis(amino-3-chlorophenyl)ethane; bis(4-amino-3,5-dimethylphenyl)methane;bis(4-amino-3,5-diethylphenyl)methane; bis(4-amino-3-ethyldiaminofluorene; diaminobenzoic acid; 2,3-diaminonaphthalene;2,3-diaminophenol; -5-methylphenyl)methane;bis(4-amino-3-methylphenyl)methane; bis(4-amino-3-ethylphenyl)methane;4,4′-diaminophenylsulfone; 3,3′-diaminophenylsulfone;2,2-bis(4,-(4-aminophenoxy)phenyl)sulfone;2,2-bis(4-(3-aminophenoxy)phenyl)sulfone; 4,4′-oxydianiline;4,4′-diaminodiphenyl sulfide; 3,4′-oxydianiline;2,2-bis(4-(4-aminophenoxy)phenyl)propane;1,3-bis(4-aminophenoxy)benzene; 4,4′-bis(4-aminophenoxy)biphenyl;4,4′-diamino-3,3′-dihydroxybiphenyl; 4,4′-diamino-3,3′-dimethylbiphenyl;4,4′-diamino-3,3′-dimethoxybiphenyl; Bisaniline M; Bisaniline P;9,9-bis(4-aminophenyl)fluorene; o-tolidine sulfone; methylenebis(anthranilic acid); 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane;1,3-bis(4-aminophenoxy)propane; 1,4-bis(4-aminophenoxy)butane;1,5-bis(4-aminophenoxy)butane; 2,3,5,6-tetramethyl-1,4-phenylenediamine;3,3′,5,5′-tetramethylbenzidine; 4,4′-diaminobenzanilide;2,2-bis(4-aminophenyl)hexafluoropropane; polyoxyalkylenediamines (e.g.Huntsman's Jeffamine D-230, D400, D-2000, and D-4000 products);1,3-cyclohexanebis(methylamine); m-xylylenediamine; p-xylylenediamine;bis(4-amino-3-methylcyclohexyl)methane; 1,2-bis(2-aminoethoxy)ethane;3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.0^(2,6))decane; and the like.

The second step of the reaction involves the condensation of theremaining amine residues with a slight excess of maleic anhydride toform the maleimide moieties. This second step can be accomplishedemploying techniques well known to those of skill in the art. The moststraightforward preparation of maleimides entails formation of themaleamic acid via reaction of the primary amine with maleic anhydride,followed by dehydrative closure of the maleamic acid with aceticanhydride. A major complication is that some or all of the closure isnot to the maleimide, but to the isomaleimide. Essentially theisomaleimide is the dominant or even exclusive kinetic product, whereasthe desired maleimide is the thermodynamic product. Conversion of theisomaleimide to the maleimide is effectively the slow step and,particularly in the case of aliphatic amines, may require forcingconditions which can lower the yield. Of course, a variety of otherapproaches can also be employed.

For example, dicyclohexylcarbodiimide (DCC) closes maleamic acids muchmore readily than does acetic anhydride. With DCC, the product isexclusively isomaleimide. However, in the presence of suitableisomerizing agents, such as 1-hydroxybenzotriazole (HOBt), the productis solely the maleimide. The function of the HOBt could be to allow theclosure to proceed via the HOBt ester of the maleamic acid (formed viathe agency of DCC) which presumably closes preferentially to themaleimide. Likely, isomerizing agents such as HOBt add to the isoimideto yield the amic acid ester. If this exhibits any tendency whatsoeverto close to the imide, much less a strong bias for doing so, a route forinterconverting isoimide and imide is thereby established and thethermodynamic product, imide, should ultimately prevail. Thus if theinitial closure of ester formed in the DCC reaction yields any isoimide,or if any isoimide is produced by direct closure of the acid, thesituation will be subsequently “corrected” via conversion of theisoimide to the imide by the action of the active ester alcohol as anisomerizing agent. An alternative method for affecting thecyclodehydration of maleamic acids is set forth in U.S. Pat. No.5,973,166, the entire contents of which are incorporated herein byreference. This method utilizes amine salts that can be successfullyused to replace the polar, aprotic solvents that have been used for thecyclodehydration of maleamic acids. The use of these salts providescompetitive reaction times and product yields relative to resultsobtained with polar, aprotic solvents. These salts have the advantage ofhaving no vapor pressure and, therefore, have no possibility toco-distill with the water produced by the cyclodehydration reaction.Furthermore, such salts can be tailored to have desirable solubilitycharacteristics (i.e., soluble in the refluxing azeotropic solvent, butinsoluble at room temperature) that permit their easy removal from thereaction product. Such salts are not destroyed during thecyclodehydration reaction and, therefore, can be efficiently recycledagain and again.

A wide variety of anhydrides are contemplated for use in the practice ofthe invention, such as, for example, polybutadiene-graft-maleicanhydride; polyethylene-graft-maleic anhydride; polyethylene-alt-maleicanhydride; polymaleic anhydride-alt-1-octadecene;polypropylene-graft-maleic anhydride; poly(styrene-co-maleic anhydride);pyromellitic dianhydride; maleic anhydride, succinic anhydride;1,2,3,4-cyclobutanetetracarboxylic dianhydride;1,4,5,8-naphthalenetetracarboxylic dianhydride;3,4,9,10-perylenentetracarboxylic dianhydride;bicyclo(2.2.2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;diethylenetriaminepentaacetic dianhydride; ethylenediaminetetraaceticdianhydride; 3,3′,4,4′-benzophenone tetracarboxylic dianhydride;3,3′,4,4′-biphenyl tetracarboxylic dianhydride; 4,4′-oxydiphthalicanhydride; 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride;2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride;4,4′-bisphenol A diphthalic anhydride;5-(2,5-dioxytetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride; ethylene glycol bis(trimellitic anhydride); hydroquinonediphthalic anhydride; allyl nadic anhydride; 2-octen-1-ylsuccinicanhydride; phthalic anhydride; 1,2,3,6-tetrahydrophthalic anhydride;3,4,5,6-tetrahydrophthalic anhydride; 1,8-naphthalic anhydride; glutaricanhydride; dodecenylsuccinic anhydride; hexadecenylsuccinic anhydride;hexahydrophthalic anhydride; methylhexahydrophthalic anhydride;tetradecenylsuccinic anhydride; and the like.

Additional anhydrides contemplated for use include, but are not limitedto:

-   -   where X is saturated or unsaturated strait or branched alkyl        polyester, polyamide, polyether, polysiloxane, polyurethane

All of the following compounds are also contemplated for use in thepractice of the invention:

Imide-extended maleimide compounds remain flexible at room temperatureand are tougher than currently available maleimide-terminated rubbers.See e.g., U.S. Pat. Nos. 7,208,566, 7,884,174 and U.S. PatentPublication No. 20110130485, the contents of which are incorporatedherein in their entirety. Thus, they may be used alone in adhesivecompositions or added to available resins as a toughening agent. Themaleimides of the invention will be present in the curable adhesivecompositions in an amount from 0.05 to 98 weight percent (wt %) based onthe organic components present (excluding any fillers).

Also contemplated for use in the invention are monomaleimides having theformula:

wherein R₁ is a substituted or an unsubstituted aliphatic, alkenyl, oraromatic moiety; and R₂ is a substituted or an unsubstituted aliphatic,alkenyl, aromatic, or siloxane moiety; and R₃ is H or methyl.

In some embodiments, each of R₁ and R₂ is independently a substituted oran unsubstituted linear, branched, or cyclic aliphatic or alkenylmoieties having from 2 to about 500 carbon atoms. In other embodiments,R₁ is a substituted or an unsubstituted aromatic or heteroaromaticmoiety having from 6 to about 14 carbon atoms.

In certain other embodiments, R₂ is a substituted or an unsubstitutedsiloxane moiety having from 2 to about 1000 silicon atoms. In someembodiments, R₂ is a polysiloxane moiety, such as, for example,dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, orcombinations thereof.

When R₁ and R₂ are substituted, the substituents present are those asset forth above.

In another embodiment of the invention, polymaleimides are contemplatedfor use in the invention including polymers having a plurality ofpendant repeating units having the structure:

wherein R₃ is a substituted or an unsubstituted aliphatic, alkenyl,aromatic, heteroaromatic, or siloxane moiety; and R₄ is H or methyl

As used herein, the term “pendant” means that the structure set forthabove is attached to a polymer main chain through at least one covalentbond.

In some embodiments, R₃ is a substituted or an unsubstituted linear,branched, or cyclic aliphatic or alkenyl moiety having from 2 to about500 carbon atoms. In other embodiments, R₃ is a substituted or anunsubstituted aromatic or heteroaromatic moiety having from 6 to about14 carbon atoms. In other embodiments, R₃ is a substituted or anunsubstituted siloxane moiety having from 2 to about 1000 silicon atoms.R₃ can also be a polysiloxane, such as, for example, dimethylsiloxane,methylphenylsiloxane, diphenylsiloxane, or combinations thereof. When R₃is substituted, the substituents are as set forth above.

In a further embodiment, polymaleimide polymers are contemplated for usein the invention, including a plurality of repeating units having thestructure:

wherein R₄ is a substituted or an unsubstituted linear, branched, orcyclic aliphatic or alkenyl moiety having from 2 to about 500 carbonatoms, or an aromatic moiety; and R₅ is H or methyl.

In some embodiments, R₄ is a substituted or an unsubstituted linear,branched, or cyclic aliphatic or alkenyl moiety having from 2 to about500 carbon atoms. In other embodiments, R₄ is a substituted or anunsubstituted aromatic or heteroaromatic moiety having from 6 to about14 carbon atoms. In other embodiments, R₄ is a substituted or anunsubstituted siloxane moiety having from 2 to about 1000 silicon atoms.R₄ can also be a polysiloxane, such as, for example, dimethylsiloxane,methylphenylsiloxane, diphenylsiloxane, methylhydrosiloxane, orcombinations thereof. When R₄ is substituted, the substituents are asset forth above.

Examples of such polymaleimides are shown in U.S. Patent Publication No.20110130485, FIG. 3 (incorporated herein by reference). The precursorpolymers or oligomers with pendant or mainchain succinic anhydridefunctional groups are known in the art. Examples of such materialsinclude polyolefins (e.g., polyethylene, polypropylene, and the like)grafted with succinic anhydride residues, polybutadiene grafted withsuccinic anhydride residues, alternating or random copolymers of maleicanhydride with styrene or α-olefins, and the like. In order to preparethe polymaleimides of the invention, a large excess of diamine istypically used in order to suppress undesirable cross-linking reactions.

The imide-extended mono-, bis, and polymaleimides of the invention maybe used independently in compositions of the invention, or may becombined with other compounds and resins.

Furthermore, the compositions of the invention can liquid imide-extendedbismaleimide monomer having the structure (I):

Which are described in U.S. Pat. No. 7,157,587, which is incorporated byreference herein in its entirety.

In the structure set forth above, the C₃₆H₇₂ aliphatic moiety is derivedfrom the hydrogenated dimer diamine Versamine 552 (Cognis), and can berepresented by the following structure:

Referring to FIG. 1 of U.S. Pat. No. 7,157,587, compound (I) is readilyprepared by a two-step, single-pot synthesis. The first step involvesthe condensation of a dianhydride (BPADA from General Electric) withdimer diamine (Versamine 552 from Cognis Corporation) to form anamine-terminated polyimide. The diamine should be present in at least aslight excess of that necessary to form the imide-linked diamineintermediate.

The second step of the reaction involves the condensation of theremaining amine residues with a slight excess of maleic anhydride toform the maleimide moieties. This second step can be accomplishedemploying techniques well known to those of skill in the art. The moststraightforward preparation of maleimides entails formation of themaleamic acid via reaction of the primary amine with maleic anhydride,followed by dehydrative closure of the maleamic acid with aceticanhydride. A major complication is that some or all of the closure isnot to the maleimide, but to the isomaleimide. Essentially theisomaleimide is the dominant or even exclusive kinetic product, whereasthe desired maleimide is the thermodynamic product. Conversion of theisomaleimide to the maleimide is effectively the slow step and,particularly in the case of aliphatic amines, may require forcingconditions which can lower the yield. Of course, a variety of otherapproaches can also be employed.

For example, dicyclohexylcarbodiimide (DCC) closes maleamic acids muchmore readily than does acetic anhydride. With DCC, the product isexclusively isomaleimide. However, in the presence of suitableisomerizing agents, such as 1-HOBt hydroxybenzotriazole (HOBt), theproduct is solely the maleimide. The function of the could be to allowthe closure to proceed via the HOBt ester of the maleamic acid (formedvia the agency of DCC) which presumably closes preferentially to themaleimide. Likely, isomerizing agents such as HOBt add to the isoimideto yield the amic acid ester. If this exhibits any tendency whatsoeverto close to the imide, much less a strong bias for doing so, a route forinterconverting isoimide and imide is thereby established and thethermodynamic product, imide, should ultimately prevail. Thus if theinitial closure of ester formed in the DCC reaction yields any isoimide,or if any isoimide is produced by direct closure of the acid, thesituation will be subsequently “corrected” via conversion of theisoimide to the imide by the action of the active ester alcohol as anisomerizing agent.

An alternative method for affecting the cyclodehydration of maleamicacids is set forth in U.S. Pat. No. 5,973,166, the entire contents ofwhich are incorporated herein by reference. This method utilizes aminesalts that can be successfully used to replace the polar, aproticsolvents that have been used for the cyclodehydration of maleamic acids.The use of these salts provides competitive reaction times and productyields relative to results obtained with polar, aprotic solvents. Thesesalts have the advantage of having no vapor pressure and, therefore,have no possibility to co-distill with the water produced by thecyclodehydration reaction. Furthermore, such salts can be tailored tohave desirable solubility characteristics (i.e., soluble in therefluxing azeotropic solvent, but insoluble at room temperature) thatpermit their easy removal from the reaction product. Such salts are notdestroyed during the cyclodehydration reaction and, therefore, can beefficiently recycled again and again.

In certain embodiments, the present invention provides chain-propagatedpolyimide polymers having a flexible aliphatic backbone in place of thetraditional aromatic ether backbone found in conventional polyimidepolymers. Although both invention polymers and conventional polymershave the same high temperature resistance due to their imide linkage,invention polyimide polymer advantageously have low modulus due to theflexible backbone. In addition, invention polyimide polymers displaylower shrinkage than conventional polyimide polymers due to the chainpropagation mechanism, thereby reducing stress on a wafer passivatedwith such polymers. Taken together, the methods and materials of theinvention reduce the potential for delamination and warpage ofsemiconductor passivating layers.

The polyimide polymers according to the invention can be used inconventional process flow for building the wafer passivation layer.Table 1 below compares the properties of the invention polyimidepolymers with those of the conventional polyimide polymers currentlyused for wafer passivation.

TABLE 1 Comparison of Invention Polyimide Polymers with ConventionalPolyimide Polymers Invention Polyimide Polymer Conventional PolyimideFlexible aliphatic backbone Stiff aromatic ether backbone Fast, chainpropagation cure mechanism Slow, ring-closing condensation curemechanism Proprietary imide-extended maleimide Non-proprietary chemistrychemistry Single component system in solvent for Two component system insolvent for spin spin coating and also available as spin- coatingcoatable (90° C.) solventless system Solventless spinning eliminatesneed for EBR typically required as well as EBR (Edge Bead Removal)backside rinse in solvent containing spin coating solutions Inherent UVactive polymer (no photo- Secondary functional group and photo-initiator needed) initiator must be added Developable in standardorganic solvents Requires caustic and corrosive high pH (supercriticalCO₂ can also be used) TMAH (tetramethylammonium hydroxide) Fully curedwith UV (post bake is Requires hard bake after optional)exposure/develop Thermal decomposition Same as Invention PolyimidePolymers temperature >400° C. Inherent high adhesion to metals,Typically requires toxic/corrosive including Au organosilanepretreatments Free radical cure in less than 15 minutes Cure is 200° C.for 30 min + 325° C. for at <185° C. (if needed) 60 minutes Low modulus<500 MPa High modulus >2000 MPa Low cure shrinkage Thickness reductionof 50-60% from deposit to hard bake

The present invention thus provides passivation layers for semiconductorwafers that include low modulus (<500 MPa) and low cure shrinkagepolyimide materials. Exemplary polyimide materials for use in themethods of the present invention are described in U.S. Pat. No.7,208,566, the contents of which is incorporated by reference herein inits entirety. For example, the experiments detailed below in Example 1utilize a maleimide functional oligomer (R1184) the synthesis of whichis outlined in Example 5 of the U.S. Pat. No. 7,208,566.

Compositions Containing Low Modulus Polyimides

The present invention provides compositions containing at least one lowmodulus polyimide compound. For example, the low modulus polyimides maybe used independently as the monomer in a polymeric composition, such asa wafer passivation composition, or may be combined with other materialsand reagents to prepare wafer passivation compositions. In certainembodiments, the low modulus polyimides may be combined with othermonomers and/or resins to prepare wafer passivation compositions. Thelow modulus polyimides may be used as the sole photoimageablethermoset/monomer of a wafer passivation composition of the invention.In other embodiments, the low modulus polyimides may be combined withother monomers, such as thermoset monomers, to make a fully formulatedwafer passivation composition.

In certain embodiments of the invention, the low modulus polyimide ispresent in a composition, such as a wafer passivation composition, in anamount from 0.5 weight percent (wt %) to about 98 wt %, based on thetotal weight of the composition. Typically, the composition will containan amount of the low modulus polyimide equal to at least about 40 wt %,often at least about 60 wt %, frequently at least about 80 wt %, and insome embodiments at least about 95 wt % based on the total weight of thecomposition (after all the solvent has been removed).

In another embodiment of the invention, the composition containing thelow modulus polyimide includes at least one co-monomer, which istypically present in an amount from 10 wt % to about 90 wt %, based onthe total weight of the composition. In some aspects of the invention,the composition will contain an amount of the co-monomer equal to atleast about 15 wt %, often at least about 20 wt %, frequently at leastabout 25 wt %, and in some embodiments at least about 30 wt % based onthe total weight of the composition. Co-monomers suitable for use in thepolyimide-containing compositions according to the invention include,but are not limited to, acrylates, acrylamides, methacrylates,methacrylamides, cyanate esters, maleimides, vinyl ethers, vinyl esters,styrenic compounds, allyl functional compounds, epoxies, epoxycuratives, and olefins.

Curing Initiators. In certain embodiments, the present inventionprovides compositions, such as adhesive compositions, including at leastone low modulus polyimide and at least one curing initiator. The curinginitiator is typically present in adhesive compositions of the inventionat an amount from 0.1 wt % to about 5 wt %, based on total weight of thecomposition, and is typically a free-radical initiator. In someembodiments, the curing initiator is present at least about 0.5 wt %,often at least about 1 wt %, frequently at least about 2 wt %, at insome embodiments at least about 3 wt %, based on total weight of thecomposition.

Free-radical initiators contemplated for use in the practice of thepresent invention typically decompose (i.e., have a half life in therange of about 10 hours) at temperatures in the range of about 70° C. upto 180° C. Exemplary free radical initiators contemplated for use in thepractice of the present invention include peroxides (e.g. dicumylperoxide, dibenzoyl peroxide, 2-butanone peroxide, tert-butylperbenzoate, di-tert-butyl peroxide,2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, bis(tert-butylperoxyisopropyl)benzene, and tert-butyl hydroperoxide), azo compounds(e.g., 2,2′-azobis(2-methyl-propanenitrile),2,2′-azobis(2-methylbutanenitrile), and1,1′-azobis(cyclohexanecarbonitrile)). Other free-radical initiatorsthat will be well-known in the art may also be suitable for use in thecompositions of the present invention.

Photoinitiators. Free radical initiators also include photoinitiators.For invention compositions that contain a photoinitiator, the curingprocess can be initiated, for example, by UV radiation. In oneembodiment, the photoinitiator is present at a concentration of 0.1 wt %to 5 wt %, based on the total weight of the organic compounds in thecomposition (excluding any filler). In one embodiment, thephotoinitiator comprises 0.5 wt % to 3.0 wt %, based on the total weightof the organic compounds in the composition. In other embodiments, thephotoinitiator is present at least about 0.5 wt %, often at least about1 wt %, frequently at least about 2 wt %, and in some embodiments atleast about 3 wt %, based on the total weight of the organic compoundsin the composition. Photoinitiators include benzoin derivatives,benzilketals, α,α-dialkoxyacetophenones, α-hydroxyalkylphenones,α-aminoalkylphenones, acylphosphine oxides, titanocene compounds,combinations of benzophenones and amines or Michler's ketone, and thelike.

In some embodiments, both photoinitiation and thermal initiation may bedesirable. For example, curing of a photoinitiator-containing adhesivecan be started by UV irradiation, and in a later processing step, curingcan be completed by the application of heat to accomplish a free-radicalcure. Both UV and thermal initiators may therefore be added to theadhesive compositions of the invention.

Additional Co-Curing Compounds. In certain aspects, the compositions,such as adhesive compositions of the invention include at least oneadditional compound that can co-cure with the low modulus polyimides.The additional compound is typically present in a wafer passivationcomposition from about 10 wt % to about 90 wt % based on total weight ofthe composition. In such aspects, the composition will typically containan amount of the co-curing compound equal to at least about 20 wt %,often at least about 30 wt %, frequently at least about 40 wt %, and insome embodiments at least about 50 wt % based on the total weight of thecomposition.

Such compounds include, for example, epoxies (e.g. epoxies based onglydicyl ethers of alcohols, phenols, bisphenols, oligomeric phenolics,phenolic novolacs, cresolic novolacs, acrylates, methacrylates,maleimides, poly-phenol compounds (e.g. poly(4-hydroxystyrene)),anhydrides, dianhydrides, polyanhydrides such as styrene-maleicanhydride co-polymers, imides, carboxylic acids, dithiols, polythiols,phenol functional mono-maleimides, bismaleimides, polymaleimides,mono-itaconates, mono-maleates, mono-fumarates, acrylic acid,methacrylic acid, cyanate esters, vinyl ethers, vinyl esters, or phenolfunctional esters, ureas, amides, polyolefins (e.g. amine, carboxylicacid, hydroxy, and epoxy functional) siloxanes (e.g. epoxy, phenolic,carboxylic acid, or thiol functional), cyanoacrylates, allyl functionalcompounds and styrenic, as well as combinations thereof. In yet furtherembodiments, the invention provides cured adhesives prepared fromcompositions that include at least one low modulus polyimide.

Coupling Agents. In certain aspects, the adhesive compositions of theinvention include at least one additional coupling agent. Exemplarycoupling agents contemplated for use in the practice of the presentinvention include silicate esters, metal acrylate salts (e.g., aluminummethacrylate), titanates (e.g., titanium methacryloxyethylacetoacetatetriisopropoxide), zirconates, or compounds that contain acopolymerizable group and a chelating ligand (e.g., phosphine,mercaptan, acetoacetate, and the like). In some embodiments, thecoupling agent contains both a co-polymerizable function (e.g., vinyl,acrylate, methacrylate, epoxy, thiol, anhydride, isocyanate, and phenolmoieties) and a silicate ester function. The silicate ester portion ofthe coupling agent is capable of condensing with metal hydroxidespresent on the mineral surface of substrate, while the co-polymerizablefunction is capable of co-polymerizing with the other reactivecomponents of invention wafer passivation compositions. In certainembodiments coupling agents contemplated for use in the practice of theinvention are oligomeric silicate coupling agents such aspoly(methoxyvinylsiloxane).

Wafer Passivation Compositions

In certain embodiments, the present invention provides wafer passivationcompositions that are of various consistencies including, liquids,solutions, pastes and thermoplastic solids. In one embodiment, the waferpassivation composition is a solution containing a fully-imidized BMIoligomer suitable for spin coating onto a wafer comprising multiplemicroelectronic devices.

In certain embodiments, a solvent may be employed in the practice of theinvention. For example, when the wafer passivation compound isspin-coated onto a circular wafer, it is desirable to have an evencoating throughout the entire wafer, i.e., the solvent or solvent systemshould have the ability to deliver the same amount of adhesive to eachpoint on the wafer. Thus, the wafer passivation compound will be evenlycoated throughout, i.e., there will be the same amount of material atthe center of the wafer as at the edges. Ideally, the solution of thewafer passivation compound is “Newtonian”, with a thixotropic slope of1.0. In certain embodiments, the solutions used to dispense the waferpassivation compound have slopes ranging from 1.0 to about 1.2.

In some embodiments, the solvent or solvent system has a boiling pointranging from about 100° C. up to about 150° C. In some embodiments, thesolvent is toluene.

In general, the wafer passivation compositions of the invention, willphotoimage under the influence of UV light at or near room temperature.All non-developed portions of the passivation film can then be removedvia soaking in, or application of a jet spray of, an appropriate solventor combination of solvents. The remaining photocured polyimide filmcould then be fully cured via a post-bake at 180-220° C. forapproximately fifteen minutes to one hour.

Inhibitors for free-radical cure may also be added to the adhesivecompositions and die-attach pastes described herein to extend the usefulshelf life. Examples of free-radical inhibitors include hindered phenolssuch as 2,6-di-tert-butyl-4-methylphenol;2,6-di-tert-butyl-4-methoxyphenol; tert-butyl hydroquinone;tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))benzene;2,2′-methylenebis(6-tert-butyl-p-cresol); and1,3,5-trimethyl-2,4,6-tris(3′,5′-di-tert-butyl-4-hydroxybenzyl)benzene.Other useful hydrogen-donating antioxidants such as derivatives ofp-phenylenediamine and diphenylamine. It is also well know in the artthat hydrogen-donating antioxidants may be synergistically combined withquinones and metal deactivators to make a very efficient inhibitorpackage. Examples of suitable quinones include benzoquinone, 2-tertbutyl-1,4-benzoquinone; 2-phenyl-1,4-benzoquinone; naphthoquinone, and2,5-dichloro-1,4-benzoquinone. Examples of metal deactivators includeN,N′-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine; oxalylbis(benzylidenehydrazide); andN-phenyl-N′-(4-toluenesulfonyl)-p-phenylenediamine. Nitroxyl radicalcompounds such as TEMPO (2,2,6,6-tetramethyl-1-piperidnyloxy, freeradical) are also effective as inhibitors at low concentrations. Thetotal amount of antioxidant plus synergists typically falls in the rangeof 100 to 2000 ppm relative to the weight of total base resin. Otheradditives, such as adhesion promoters, in types and amounts known in theart, may also be added.

Properties of Wafer Passivation Coatings Containing Low ModulusPolyimides

Advantageously, the low modulus, imide-extended BMI compounds of theinvention can impart many properties that are desirable in a passivationcoating. Historically, polyimide coatings for wafer passivation havebeen based on high T_(g) resins that are either formed in situ on thewafer surface via cyclodehydration of their amic acid precursors, or ifpre-imidized, are only soluble in high boiling, expensive solvents suchas N-methyl-2-pyrrolidone (NMP) which is difficult to remove from thefinal film. The passivation layer compositions of the invention containlow modulus, imide-extended BMI compounds that are fully imidizedoligomers and can be spin coated onto the wafer either neat or dissolvedin a variety of low cost, readily available solvents. The imide-extendedBMI compounds of this invention are also intrinsically photoimagable anddo not require the addition of photoinitiators in order to cure undermid-range UV light. The compounds of this invention are intrinsicallyhydrophobic and have significantly lower moisture absorption when fullycured than the traditional polyimide coatings, which can absorb as muchas 4-5% moisture by weight. Furthermore, the compounds of this inventionprovide low modulus coatings after cure and thus are much better suitedfor use on thinned silicon devices.

The polyimide resins of this invention cure to low modulus films. Themodulus of these films, post cure, is less than about 2,000 MPa at 25°C., such as less than about 1,000 MPa at 25° C., for example, less thanabout 100 MPa at 25° C., e.g., less than about 25 MPa at 25° C.

The invention will now be further described with reference to by thefollowing illustrative, non-limiting examples.

EXAMPLES Example 1 Elongation/Breaking Strength—Dogbone Samples onInstron

Tensile strength and elongation were measured on an imide-extendedbismaleimide resin that had been prepared according to U.S. Pat. No.7,208,566 in order to demonstrate the mechanical characteristics ofcompositions of the invention. The resin used in this example wasprepared according to Example 5 of that U.S. Pat. No. 7,208,566. Theresin had been precipitated into acetone to remove any remaining lowermolecular weight residues. In this form (designated as R1130) theapproximate molecular weight of the imide extended bismaleimide isaround 3,000 Daltons (and is therefore also known as BMI-3000). In thisexample, two cure conditions were examined: (a) cured via UV exposureonly, and (b) UV exposure followed by a thermal post reaction. The UVprocess parameters were not optimized for intensity, wavelength orprotection from O₂ inhibition. Specimen dimensions were: 13 mm wide×1.3mm thick. The photoinitiator (when present) in this example and in allother examples that follow was Irgacure 819 (Ciba). The thermalinitiator (when present) in this example and in all other examples thatfollow was dicumyl peroxide (DCP).

The results in Table 2 show that the tensile strength of the UV-onlycured material is 7.7 MPa and has 113% elongation. Both the tensilestrength and the elongation of the UV cured material increased by about40% after a three-hour heat treatment at 175° C. in the presence ofone-weight percent DCP. This may be a result of the relatively thickdogbone specimen required for Instron testing or the specimen could havebeen under cured using the UV exposure conditions in this experiment.The final numbers demonstrate that the invention material has lowerstrength but more elongation than standard polyimides. This demonstratesthat compositions of the invention are suited to use as low stresspassivation layers.

TABLE 2 Test Results for Dogbone Samples of BMI Breaking Elongation,Formulation Cure Condition Strength, MPa % R1130 + 30 min. UV 7.7 1130.5% UV initiator R1130 + 30 min. UV + 11.1 154 0.5% UV initiator + 3 hrat 175° C. 1% DCP

Example 2 Trials Using Toluene as the Image Development Solvent

FIGS. 1-3 show the performance of the materials of the invention in theadditional trials that illustrate the applicability of the compositionsof the invention to photoimaging applications. Additional trials wereperformed using the low modulus, imide-extended BMI. Here and below,compound R1184, which was used as such imide-extended BMI, is thecompound described in Example 5 of the above-mentioned U.S. Pat. No.7,208,566, without a subsequent precipitation step, the compound havinga molecular weight of about 2,000 Daltons. Compound R1184 wasdoctor-bladed onto ceramic wafers to form an even coating, followed byUV exposures through masks. The doctor-bladed films were exposed to abroad-spectrum UV light source with the mask interposed between theun-cured film and the light source. The photoimaged films were thendeveloped using a jet of toluene.

The circular areas in the developed images directly correspond to opaqueareas of the mask. The areas of the imide-extended BMI film surroundingthe circular holes correspond to transparent areas in the mask. Thephotoimaging process followed by development reproduced the pattern ofthe mask with excellent fidelity. FIG. 1 (8 mil dots, 20 mil spacing)shows the developed photoimaged film in which the mask had 8 mildiameter opaque dots with 20 mil center-to-center spacing. The developedfilm has 7.8 mil circular holes with 19.2 mil spacing between holes.FIG. 2 (5 mil dots, 10 mil spacing) shows a developed film that has 4.6mil holes and 9.5 mil spacing between holes (the nominal values for themask were 5 mils and 10 mils, respectively). FIG. 3 (3 mil dots, 10 milspacing) shows a developed film with 3.4 mil holes and 10 mil spacing(the mask nominal values were 3 mils and 10 mils, respectively).

Toluene is effective at removing uncured BMI oligomer, however, itcontinues to prove to be aggressive towards UV-cured BMI resin as well,even towards a BMI oligomer with the crosslinking bolstered by anadditional 10% of R1091 (X-BMI) described below. This fact is manifestedby its ability to plasticise and/or loosen the grip of the films onsubstrates. Acetone appears to be a better choice as an imagedevelopment solvent, in that it has sufficient solvent power to dissolvethe unexposed areas of the film, but does not plasticise the exposedareas.

R1091 is X-BMI, which is dimer diamine BMI prepared as described in U.S.Pat. No. 5,973,166, the entire contents of which is incorporated byreference herein. X-BMI is a product which is described in U.S. Pat. No.5,973,166 (see Example 6 of this U.S. patent, the fourth product inTable 2).

Example 3 Trials Using Cyclohexanone as the Image Development Solvent

Cyclohexanone proved to be a suitable solvent for developing photoimagedpatterns in compositions of the invention. In this example, the film wasspin coated on wafers to achieve 13 um thickness. Coating conditionswere: (1) spin 30 seconds at 590 rpm; (2) spin 30 seconds at 1196 rpm;(3) bake 30 minutes at 100° C. (surface is non-tacky). The imaged anddeveloped pattern was characterized using a contact profilometer. In allcases, the replication of mask dimension in the imaged pattern wasexcellent with very good edge definition. Some of the developing withcyclohexanone was done using s spray device, but flooding followed by asimple rinse with acetone was just as effective. This demonstrates thatcompositions of the invention are suited to use as photoimagablepassivation layers.

Example 4 Thermogravimetric Analysis (TGA)

Percent weight loss was measured using thermogravimetric analysis (TGA)in order to demonstrate the thermal stability of compositions of theinvention. Specimens for this example were made using the same mold andmethods as in Example 1, i.e., two cure conditions were examined: (a)cured via UV exposure only, and (b) UV exposure followed by a thermalpost reaction. The UV process parameters were not optimized forintensity, wavelength or protection from O₂ inhibition. Specimendimensions were: 13 mm wide×1.3 mm thick.

The TGA results in Table 3 show that the percent weight loss of theUV-only cured material tends to be slightly higher than the materialwith the UV plus thermal post cure. This may be a result of therelatively thick dogbone mold used here (required for Instron testing)could have been under cured using the UV exposure conditions in thisexperiment. A fresh sample of the UV-only cured material was run andshowed good repeatability of the original weight loss ramp to 400° C.,but in this case the TGA was programmed to cool to room temperature thenimmediately ramp back up again to 400° C. On this second ramp to 400° C.the percent weight loss was significantly reduced.

TABLE 3 TGA Results Decomposition Weight Loss, %, At a TemperatureTemperature, Formulation Cure Conditions 100° C. 200° C. 260° C. 300° C.400° C. ° C. R1130 + 0.5% 30 min. UV 0.34 0.90 1.08 1.70 4.04 471 UVinitiator R1130 + 0.5% 30 min. UV + 0.00 0.23 0.95 1.58 2.93 464 UVinitiator + 3 hr at 175° C. 1% DCP

The results of the first and second ramp are shown in Table 4. Again,the UV process parameters were not optimized for intensity, wavelengthor protection from O₂ inhibition. Specimen dimensions for UV exposurewere: 13 mm wide×1.3 mm thick. Percentage of weight change shown inTable 4 is based on starting weight of each scan. The initial scan startweight was 8.878 mg and the second scan start weight was 8.534 mg.

The results shown in Table 4 indicate that after the more volatile undercured monomers were eliminated on the first ramp to 400° C., theremaining, cured polymer exhibited excellent thermal stability duringthe second ramp to 400° C. Overall, the TGA results demonstrate that theinvention material has thermal stability at least equivalent to standardpolyimides. Additional TGA testing yielded similar results on a sampleusing the following materials: R1184+2% DCP UV cured 30 minutes followedby 1 hour at 180° C.

TABLE 4 Weight Change Before and After Exposure to 400° C. Using TGAWeight Change, %, At a Temperature Formulation Cure Conditions 100° C.200° C. 260° C. 300° C. 400° C. R1130 + 0.5% 30 min. UV +0.007 −0.145−0.434 −0.955 −3.723 UV initiator R1130 + 0.5% Cool the sample above+0.042 +0.022 −0.018 −0.060 −0.644 UV initiator to room temperature andrepeat the TGA scan

Example 5 Thermo-analysis (DMA)

Modulus and the glass transition temperature T_(g) of compositions ofthe invention were measured using dynamic mechanical analysis (DMA). Twocure conditions were examined: (a) cured via UV exposure only, and (b)UV exposure followed by a thermal post reaction. Again, the UV processparameters were not optimized for intensity, wavelength or protectionfrom O₂ inhibition. Specimen dimensions were: 6.2 mm wide×0.6 mm thick.In this case, the specimens were molded as thin films, not thickdogbones, so there was very little difference observed in the resultsbetween the two cure conditions. The DMA results provided in Table 5show that the modulus is much lower than standard polyimides(typically, >2,000 MPa at 25° C.) and that the Tg is near roomtemperature. This suggests that the cured invention polyimide is a lowstress material for passivation.

TABLE 5 Modulus and T_(g) Data Obtained by Using DMA E′ Units, MPa, At aTemperature Cure 25° 150° 260° T_(g), Formulation Conditions C. C. C. °C. R1184 30 min. UV 146 4 6 19 (no additives) R1130 + 15 min. UV + 154 3<1 <25 0.5% UV initiator + 1 hr at 175° C. 1% DCP

The DMA scan of another formulation prepared using the followingmaterials: R1184+2% DCP; UV cured 30 minutes followed by 1 hour at 180°C. The temperature sweep was run from 25° C. to 305° C. and three seriesof data points were collected: E′ (elastic, or storage modulus); E″(loss modulus); and tan delta (the ratio of E′/E″). The peak in the tandelta series indicates that the glass transition temperature was about35° C. The room temperature modulus was around 160 MPa (1 dyn/cm²=10 Pa,& 1 MPa=1,000,000 Pa).

Example 6 Moisture Uptake

Weight gain after water immersion was measured in order to demonstratethe hydrophobicity of compositions of the invention. In this example,two water immersion test conditions are reported in Table 6 which showsthe moisture saturation content did not exceed 1% weight gain. Curetimes varied from 120 to 216 hours. The rate to reach saturation wasobserved to be quite slow, i.e., in the 80° C. test condition it took 24hours to reach saturation. This clearly demonstrates that the curedinvention polyimide is hydrophobic.

TABLE 6 Moisture Uptake Results Cure Water Immersion Weight FormulationCondition Condition Gain, % R1130 + 1% DCP 140° C. 288 hours at 80° C.0.4% R1130 + 1% DCP 140° C.  65 hours at 150° C. 0.8%

Example 7 Deformation Under Pressure

Thermal Mechanical Analysis (TMA) was used to demonstrate that curedcompositions of the invention will have resistance to flow underpressure. In this example, two test conditions were achieved by placingtwo mass loads (5 grams and 20 grams) on separate cured specimens andramping them from 100° C. to 350° C. while monitoring the deflection ofthe TMA probe. No deformation or deflection was observed at either testcondition. Formulation used was melt mixed R1130+1.0% DCP then cured 3.5hr at 175° C. Maximum pressure achieved in these experiments was about70 g/cm² with zero flow or deflection observed up to 350° C. This resultdemonstrated that the cured invention polyimide was very resistant toflow over the entire temperature range of the experiment. FIG. 4 showsthree different wafer/passivating layer combinations, each inperspective and cross-section views. As can be seen from FIG. 4, in someexemplary devices 10 of the present invention, the passivating layer 100can be disposed on the top of the wafer 105, the passivating layer 100comprising the holes 110. The embodiments depicted on FIGS. 4A and 4Bshow schematically a fully encapsulated wafer 105; the embodimentsdepicted on FIGS. 4C and 4D show the a section of the center of wafer105 (having its ends removed); and the devices 10 depicted on FIGS. 4Eand 4F illustrate the same center with the holes 110 in the passivatinglayer 100 formed by photolithography.

Example 8 Vertical Shrinkage

Minimal dimensional change during the wafer coating process is animportant feature for making passivation films and especially forbuilding up dielectric interlayers. Typically, polyimides are formed insitu through cyclodehydration of the polyamic acid precursors. Thisimidization step also requires the evaporation of high boiling, polaraprotic solvents. As a result, film thickness reduction of 50-60% canoccur from deposit to hard bake. This invention utilizes free radicalinitiation of chain propagation and extension during the cure reaction.

Film thickness was measured in order to demonstrate the minimal verticalshrinkage of compositions of the invention. In this example, two partswere built and measured for thickness at four locations each at fourdifferent stages of the coat and cure process: (a) after spin coat anddry; (b) after UV cure; (c) after image developing in cyclohexanone; and(d) after bake. The thickness values are presented in Table 7. Overallvertical shrinkage throughout the process was <1.5% with very littleswelling observed after solvent developing. This clearly demonstratesthat the cured invention polyimide is a low shrinkage polymer.Formulation used in this example: 50% R1130 in toluene+0.5% UVInitiator+1.0% DCP; viscosity≅300 cPs.

TABLE 7 BMI-3000 Formulation was tested for Vertical Shrinkage.Thickness, μm, Thickness, μm, Thickness, μm, Part after Spin CoatThickness, μm, after Develop 1 after Bake Num- and Dry 30 after UV Cureminute dip in 60 minutes at ber minutes at 90° 15 minutes Cyclohexanone200° C. 1 9.99 ± 0.11 10.24 ± 0.14 10.22 ± 0.16 9.84 ± 0.12 2 9.99 ±0.49 10.24 ± 0.47 10.18 ± 0.50 9.85 ± 0.47

Example 9 Degree of Planarization (DOP)

An initial pattern of 250 μm lines and spaces was coated, imaged andcured to 11 μm thickness using a composition of the invention material.The topography of this initial pattern was then characterized byscanning with a profilometer. A second layer was coated, UV cured, butnot imaged over the initial patterned layer. Subsequent profilometerscans indicate that the degree of planarization achieved was DOP=98.7%after the UV cure of the second coating. A post bake at 200° C. for 60minutes increased the DOP=99.1% for the second coating. The formulationused in this example was: 50% R1130 in toluene+0.5% UV Initiator+1.0%DCP; viscosity≅300 cPs. This demonstrates that the cured inventionpolyimide is capable of planarizing underlying topography.

Example 10 Warpage and Residual Stress

Warpage after wafer coat and cure was measured in order to calculate theresidual stress induced by compositions of the invention. In thisexample, three 200 mm diameter silicon wafers having the thickness of725 μm were spin coated at three different coating thicknesses. Eachcoating was dried 30 minutes at 60° C. and then cured for 60 minutes at175° C. (N₂ purge oven). The formulation used in this example was: 40%BMI 3000 in toluene with 0.8% DCP peroxide; viscosity=123 cPs.

The results are provided in table 8. Wafer bow changed from flat toconcave (smiley face) after cure and was less than 11 μm in all cases.Average residual stress was calculated to be 1.9±0.2 MPa using theStoney Equation (see, Felix Lu, “Physical Mechanisms of Residual Stressin Metallic Thin Films” Feb. 19, 2008 Applied Quantum Technologies/DukeUniversity, 24 pages). Wafers using standard polyimides are reported tohave concave bow of >20 μm and residual stress of about 25 MPa. Thisdemonstrates that the cured invention polyimide is low stress.

TABLE 8 BMI-3000 Warpage and Residual Stress Wafer Number 1 2 3 Spin,rpm 1,000 2,000 3,000 Coating Thickness, μm 10.64 8.38 6.3 Final Bow, μm6.8 4.4 3.7 Residual Stress, MPa 2.06 1.70 1.90

Example 11 Crosslinking Conversion—UV Cure with and withoutPhotoinitiator

The thermoset cure reaction mechanism for the invention is free radicalinitiation at the carbon-carbon double bond in the maleimide functiongroups followed by chain propagation as the maleimide crosslinks byforming a carbon-carbon single bond to another maleimide containingmonomer. The extent of cure, then, can be tracked by following theconversion in the maleimide of carbon-carbon double bonds tocarbon-carbon single bonds. In this example, FTIR was used to track theabsorbance of the carbon-carbon double bond vibrational energies inmaleimide at 827 (out-of-plane bending mode for —C—H) and 696 in-planedeformation of maleimide ring) wavenumbers as a function of UV exposuretime. The sample method used was reflectance spectroscopy obtained froma thin film dried on an ATR crystal and then placed directly in the UVexposure chamber. One composition of the invention in this example wasformulated with 0.5% of a photoinitiator to catalyze the formation offree radicals, which in turn result in polymerization of the maleimidefunctional groups in the BMI-3000. The cure energy density of the UV at365 nm was 650 mJ/cm². The reduction in absorbance at 696 wavenumbersshown in Table 9 correlates with increasing exposure time and indicatesthat crosslinking is occurring and that there is nearly 100% cureconversion after 30 minutes of UV exposure.

TABLE 9 Tracking Cross-linking Conversion Using FTIR for BMI-3000Formulations Relative Area Relative Area UV Exposure of 696 cm⁻¹ of 696cm⁻¹ Time, Peak with no Peak with 0.5% minutes PhotoinitiatorPhotoinitiator 0 100.0 100.0 1 82.0 72.4 5 35.1 22.1 15 4.8 2.8 30 1.10.5

Example 12 Crosslinking Conversion—UV Cure without Photoinitiator

This example is an extension of Example 11. The composition of theinvention in this example did not contain a photoinitiator. The BMI ofthe invention is inherently photoactive and therefore does not require aphotoinitiator to generate free radicals at the maleimide during UVexposure. As described above in Example 11, the extent of cure can betracked using FTIR to follow the conversion in the maleimide ofcarbon-carbon double bonds to carbon-carbon single bonds. In thisexample, FTIR is used to track the absorbance of the carbon-carbondouble bond vibrational energies in maleimide at 827 and 696 wavenumbersas a function of UV exposure time.

The reduction in absorbance at 696 wavenumbers shown in Table 9correlates with increasing exposure time and indicates that crosslinkingis occurring even without a photoinitiator and that there is nearly 100%cure conversion after 30 minutes of UV exposure. The inclusion of aphotoinitiator therefore produced a slight increase in the initialreaction rate, but both systems, with and without photoinitiator, canachieve the same final UV cure.

Example 13 Crosslinking Conversion—Thermal Cure with Dicumyl Peroxide

This example is an extension of Example 11. The composition of theinvention in this example was formulated to contain a peroxide freeradical initiator in place of a photoinitiator. The cure mechanismremains the same, but thermal energy is used to activate the peroxidecatalyst, not UV energy. As described above in Example 11, the extent ofcure can be tracked using FTIR to follow the conversion in the maleimideof carbon-carbon double bonds to carbon-carbon single bonds. In thisexample, FTIR is used to track the absorbance of the carbon-carbondouble bond vibrational energies in maleimide at 827 and 696 wavenumbersbefore and after a thermal bake (no UV exposure).

The sample method used was a thin film dried on a NaCl plate andtransmission spectra collected before and after bake at 200° C. for 60minutes in air convection oven. The Relative Area of the 696 cm⁻¹ peakchanged from 100.0 to 0.5 after the bake. The reduction in absorbanceobserved before and after bake indicates that crosslinking is occurringand that there is nearly 100% cure conversion after a thermal cure asthere had also been with UV cure.

Although only a few embodiments have been described in detail andexemplified above, those having ordinary skill in the art will clearlyunderstand that many modifications are possible in the describedembodiments without departing from the teachings thereof. All suchmodifications are intended to be encompassed within the followingclaims.

What is claimed is:
 1. A device, comprising a semiconductor wafer and apassivating layer disposed on the surface of the wafer, wherein thepassivating layer is comprised of a polyimide polymer comprising astructure selected from the group consisting of structures I, II andIII:

wherein: each of R, R₃ and Q is independently selected from the groupconsisting of substituted or unsubstituted aliphatic, alkenyl, aromatic,heteroaromatic and siloxane moieties; R₂ in each of structures I, II andIII is independently selected from the group consisting of H or methyl;R₄ is selected from the group consisting of substituted or unsubstitutedlinear, branched, cyclic aliphatic or alkenyl moieties having between 2and about 500 carbon atoms, and substituted or unsubstituted aromaticmoieties; n is an integer having the value between 1 to about 10; andthe symbol “

” depicts a macromolecular chain to which the structure II or III iscovalently attached, with the further proviso that in the polyimidepolymer, the molecular weight fraction of the combined contents ofnitrogen and oxygen is less than about 20%.
 2. The device of claim 1,wherein the molecular weight fraction of the combined contents ofnitrogen and oxygen is less than about 15%.
 3. The device of claim 1,wherein the molecular weight fraction of the combined contents ofnitrogen and oxygen is less than about 12%.
 4. The device of claim 1,wherein each of R, R₃ and Q is independently selected from the groupconsisting of substituted or unsubstituted aromatic or heteroaromaticmoieties having between 6 and about 14 carbon atoms.
 5. The device ofclaim 1, wherein each of R, R₃ and Q is independently selected from thegroup consisting of substituted or unsubstituted siloxane moietieshaving between 2 and about 50 silicon atoms.
 6. The device of claim 1,wherein the siloxane moiety is a polysiloxane.
 7. The device of claim 6,wherein the polysiloxane comprises repeating units selected from thegroup consisting of dimethylsiloxane, methylphenylsiloxane,diphenylsiloxane and combinations thereof.
 8. The device of claim 1,wherein substituted aliphatic, aromatic, heteroaromatic, or siloxanemoieties comprise substituents selected from the group consisting of analkyl, an alkenyl, an alkynyl, hydroxyl, oxo, an alkoxy, mercapto, acycloalkyl, a substituted cycloalkyl, a heterocyclic, a substitutedheterocyclic, an aryl, a substituted aryl, a heteroaryl, a substitutedheteroaryl, an aryloxy, a substituted aryloxy, a halogen, a haloalkyl,cyano, nitro, nitrone, an amino, an amido, —C(O)H, —C(O)—, —C(O)—, —S—,—S(O)₂—, —OC(O)—O—, —NR—C(O)—, —NR—C(O)—NR—, and —OC(O)—NR—, wherein Rselected from the group consisting of is H, a lower alkyl, an acyl, anoxyacyl, carboxyl, carbamate, sulfonyl, sulfonamide and sulfuryl.
 9. Thedevice of claim 1, wherein the polyimide forming the passivating layercures to form a film having, post cure, the modulus that is less thanabout 2,000 MPa at 25° C.
 10. The device of claim 9, wherein the modulusis less than about 1,000 MPa at 25° C.
 11. The device of claim 9,wherein the modulus is less than about 100 MPa at 25° C.
 12. The deviceof claim 9, wherein the modulus is less than about 25 MPa at 25° C. 13.A method for fabricating a device of claim 1, comprising: (a) depositinga layer of a polyimide polymer on the surface of the semiconductorwafer; and (b) curing the polyimide polymer, to thereby form a polyimidepassivating layer on the surface of a semiconductor wafer, wherein thepolyimide polymer comprises a structure selected from the groupconsisting of structures I, II and III:

wherein: each of R, R₃ and Q is independently selected from the groupconsisting of substituted or unsubstituted aliphatic, alkenyl, aromatic,heteroaromatic and siloxane moieties; R₂ in each of structures I, II andIII is independently selected from the group consisting of H or methyl;R₄ is selected from the group consisting of substituted or unsubstitutedlinear, branched, cyclic aliphatic or alkenyl moieties having between 2and about 500 carbon atoms, and substituted or unsubstituted aromaticmoieties; n is an integer having the value between 1 to about 10; andthe symbol “

” depicts a macromolecular chain to which the structure II or III iscovalently attached, with the further proviso that in the polyimidepolymer, the molecular weight fraction of the combined contents ofnitrogen and oxygen is less than about 20%, to thereby fabricate thedevice.
 14. The method of claim 13, wherein the molecular weightfraction of the combined contents of nitrogen and oxygen is less thanabout 15%.
 15. The method of claim 13, wherein the molecular weightfraction of the combined contents of nitrogen and oxygen is less thanabout 12%.
 16. The method of claim 13, wherein each of R, R₃ and Q isindependently selected from the group consisting of substituted orunsubstituted aromatic or heteroaromatic moieties having between 6 andabout 14 carbon atoms.
 17. The method of claim 13, wherein each of R, R₃and Q is independently selected from the group consisting of substitutedor unsubstituted siloxane moieties having between 2 and about 50 siliconatoms.
 18. The method of claim 13, wherein the siloxane moiety is apolysiloxane.
 19. The method of claim 18, wherein the polysiloxanecomprises repeating units selected from the group consisting ofdimethylsiloxane, methylphenylsiloxane, diphenylsiloxane andcombinations thereof.
 20. The method of claim 13, wherein substitutedaliphatic, aromatic, heteroaromatic, or siloxane moieties comprisesubstituents selected from the group consisting of an alkyl, an alkenyl,an alkynyl, hydroxyl, oxo, an alkoxy, mercapto, a cycloalkyl, asubstituted cycloalkyl, a heterocyclic, a substituted heterocyclic, anaryl, a substituted aryl, a heteroaryl, a substituted heteroaryl, anaryloxy, a substituted aryloxy, a halogen, a haloalkyl, cyano, nitro,nitrone, an amino, an amido, —C(O)H, —C(O)—, —C(O)—, —S—, —S(O)₂—,—OC(O)—O—, —NR—C(O)—, —NR—C(O)—NR—, and —OC(O)—NR—, wherein R selectedfrom the group consisting of is H, a lower alkyl, an acyl, an oxyacyl,carboxyl, carbamate, sulfonyl, sulfonamide and sulfuryl.
 21. The deviceof claim 1, wherein the polyimide polymer is obtained by a processcomprising the condensation of a dimer diamine with a dianhydride,wherein: (a) the dimer diamine is selected from the group consisting of1,10-diaminodecane; 1,12-diaminododecane; dimer diamine;1,2-diamino-2-methylpropane; 1,2-diaminocyclohexane; 1,2-diaminopropane;1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane;1,7-diaminoheptane; 1,8-diaminomenthane; 1,8-diaminooctane;1,9-diaminononane; 3,3′-diamino-N-methyldipropylamine;diaminomaleonitrile; 1,3-diaminopentane; 9,10-diaminophenanthrene;4,4′-diaminooctafluorobiphenyl; 3,5-diaminobenzoic acid;3,7-diamino-2-methoxyfluorene; 4,4′-diaminobenzophenone;3,4-diaminobenzophenone; 3,4-diaminotoluene; 2,6-diaminoanthroquinone;2,6-diaminotoluene; 2,3-diaminotoluene; 1,8-diaminonaphthalene;2,4-diaminotoluene; 2,5-diaminotoluene; 1,4-diaminoanthroquinone;1,5-diaminoanthroquinone; 1,5-diaminonaphthalene;1,2-diaminoanthroquinone; 2,4-cumenediamine; 1,3-bisaminomethylbenzene;1,3-bisaminomethylcyclohexane; 2-chloro-1,4-diaminobenzene;1,4-diamino-2,5-dichlorobenzene; 1,4-diamino-2,5-dimethylbenzene;4,4′-diamino-2,2′-bistrifluoromethylbiphenyl;bis(amino-3-chlorophenyl)ethane; bis(4-amino-3,5-dimethylphenyl)methane;bis(4-amino-3,5-diethylphenyl)methane; bis(4-amino-3-ethyldiaminofluorene; diaminobenzoic acid; 2,3-diaminonaphthalene;2,3-diaminophenol; -5-methylphenyl)methane;bis(4-amino-3-methylphenyl)methane; bis(4-amino-3-ethylphenyl)methane;4,4′-diaminophenylsulfone; 3,3′-diaminophenylsulfone;2,2-bis(4,-(4-aminophenoxy)phenyl)sulfone;2,2-bis(4-(3-aminophenoxy)phenyl)sulfone; 4,4′-oxydianiline;4,4′-diaminodiphenyl sulfide; 3,4′-oxydianiline;2,2-bis(4-(4-aminophenoxy)phenyl)propane;1,3-bis(4-aminophenoxy)benzene; 4,4′-bis(4-aminophenoxy)biphenyl;4,4′-diamino-3,3′-dihydroxybiphenyl; 4,4′-diamino-3,3′-dimethylbiphenyl;4,4′-diamino-3,3′-dimethoxybiphenyl; Bisaniline M; Bisaniline P;9,9-bis(4-aminophenyl)fluorene; o-tolidine sulfone; methylenebis(anthranilic acid); 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane;1,3-bis(4-aminophenoxy)propane; 1,4-bis(4-aminophenoxy)butane;1,5-bis(4-aminophenoxy)butane; 2,3,5,6-tetramethyl-1,4-phenylenediamine;3,3′,5,5′-tetramethylbenzidine; 4,4′-diaminobenzanilide;2,2-bis(4-aminophenyl)hexafluoropropane; polyoxyalkylenediamines (e.g.Huntsman's Jeffamine D-230, D400, D-2000, and D-4000 products);1,3-cyclohexanebis(methylamine); m-xylylenediamine; p-xylylenediamine;bis(4-amino-3-methylcyclohexyl)methane; 1,2-bis(2-aminoethoxy)ethane and3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.0^(2,6))decane; and (b) thedianhydride is selected from the group consisting ofpolybutadiene-graft-maleic anhydride; polyethylene-graft-maleicanhydride; polyethylene-alt-maleic anhydride; polymaleicanhydride-alt-1-octadecene; polypropylene-graft-maleic anhydride;poly(styrene-co-maleic anhydride); pyromellitic dianhydride; maleicanhydride, succinic anhydride; 1,2,3,4-cyclobutanetetracarboxylicdianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride;3,4,9,10-perylenentetracarboxylic dianhydride;bicyclo(2.2.2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;diethylenetriaminepentaacetic dianhydride; ethylenediaminetetraaceticdianhydride; 3,3′,4,4′-benzophenone tetracarboxylic dianhydride;3,3′,4,4′-biphenyl tetracarboxylic dianhydride; 4,4′-oxydiphthalicanhydride; 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride;2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride;4,4′-bisphenol A diphthalic anhydride;5-(2,5-dioxytetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride; ethylene glycol bis(trimellitic anhydride); hydroquinonediphthalic anhydride; allyl nadic anhydride; 2-octen-1-ylsuccinicanhydride; phthalic anhydride; 1,2,3,6-tetrahydrophthalic anhydride;3,4,5,6-tetrahydrophthalic anhydride; 1,8-naphthalic anhydride; glutaricanhydride; dodecenylsuccinic anhydride; hexadecenylsuccinic anhydride;hexahydrophthalic anhydride; methylhexahydrophthalic anhydride;tetradecenylsuccinic anhydride;

wherein X is selected from the group consisting of a saturated or anunsaturated straight-chained or branched alkyl polyester, polyamide,polyether, polysiloxane and polyurethane.
 22. The method of claim 13,wherein the passivating layer-forming polyimide polymer is obtained by aprocess comprising the condensation of a dimer diamine with adianhydride, wherein: (a) the dimer diamine is selected from the groupconsisting of 1,10-diaminodecane; 1,12-diaminododecane; dimer diamine;1,2-diamino-2-methylpropane; 1,2-diaminocyclohexane; 1,2-diaminopropane;1,3-diaminopropane; 1,4-diaminobutane; 1,5-diaminopentane;1,7-diaminoheptane; 1,8-diaminomenthane; 1,8-diaminooctane;1,9-diaminononane; 3,3′-diamino-N-methyldipropylamine;diaminomaleonitrile; 1,3-diaminopentane; 9,10-diaminophenanthrene;4,4′-diaminooctafluorobiphenyl; 3,5-diaminobenzoic acid;3,7-diamino-2-methoxyfluorene; 4,4′-diaminobenzophenone;3,4-diaminobenzophenone; 3,4-diaminotoluene; 2,6-diaminoanthroquinone;2,6-diaminotoluene; 2,3-diaminotoluene; 1,8-diaminonaphthalene;2,4-diaminotoluene; 2,5-diaminotoluene; 1,4-diaminoanthroquinone;1,5-diaminoanthroquinone; 1,5-diaminonaphthalene;1,2-diaminoanthroquinone; 2,4-cumenediamine; 1,3-bisaminomethylbenzene;1,3-bisaminomethylcyclohexane; 2-chloro-1,4-diaminobenzene;1,4-diamino-2,5-dichlorobenzene; 1,4-diamino-2,5-dimethylbenzene;4,4′-diamino-2,2′-bistrifluoromethylbiphenyl;bis(amino-3-chlorophenyl)ethane; bis(4-amino-3,5-dimethylphenyl)methane;bis(4-amino-3,5-diethylphenyl)methane; bis(4-amino-3-ethyldiaminofluorene; diaminobenzoic acid; 2,3-diaminonaphthalene;2,3-diaminophenol; -5-methylphenyl)methane;bis(4-amino-3-methylphenyl)methane; bis(4-amino-3-ethylphenyl)methane;4,4′-diaminophenylsulfone; 3,3′-diaminophenylsulfone;2,2-bis(4,-(4-aminophenoxy)phenyl)sulfone;2,2-bis(4-(3-aminophenoxy)phenyl)sulfone; 4,4′-oxydianiline;4,4′-diaminodiphenyl sulfide; 3,4′-oxydianiline;2,2-bis(4-(4-aminophenoxy)phenyl)propane;1,3-bis(4-aminophenoxy)benzene; 4,4′-bis(4-aminophenoxy)biphenyl;4,4′-diamino-3,3′-dihydroxybiphenyl; 4,4′-diamino-3,3′-dimethylbiphenyl;4,4′-diamino-3,3′-dimethoxybiphenyl; Bisaniline M; Bisaniline P;9,9-bis(4-aminophenyl)fluorene; o-tolidine sulfone; methylenebis(anthranilic acid); 1,3-bis(4-aminophenoxy)-2,2-dimethylpropane;1,3-bis(4-aminophenoxy)propane; 1,4-bis(4-aminophenoxy)butane;1,5-bis(4-aminophenoxy)butane; 2,3,5,6-tetramethyl-1,4-phenylenediamine;3,3′,5,5′-tetramethylbenzidine; 4,4′-diaminobenzanilide;2,2-bis(4-aminophenyl)hexafluoropropane; polyoxyalkylenediamines (e.g.Huntsman's Jeffamine D-230, D400, D-2000, and D-4000 products);1,3-cyclohexanebis(methylamine); m-xylylenediamine; p-xylylenediamine;bis(4-amino-3-methylcyclohexyl)methane; 1,2-bis(2-aminoethoxy)ethane and3(4),8(9)-bis(aminomethyl)tricyclo(5.2.1.0^(2,6))decane; and (b) thedianhydride is selected from the group consisting ofpolybutadiene-graft-maleic anhydride; polyethylene-graft-maleicanhydride; polyethylene-alt-maleic anhydride; polymaleicanhydride-alt-1-octadecene; polypropylene-graft-maleic anhydride;poly(styrene-co-maleic anhydride); pyromellitic dianhydride; maleicanhydride, succinic anhydride; 1,2,3,4-cyclobutanetetracarboxylicdianhydride; 1,4,5,8-naphthalenetetracarboxylic dianhydride;3,4,9,10-perylenentetracarboxylic dianhydride;bicyclo(2.2.2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride;diethylenetriaminepentaacetic dianhydride; ethylenediaminetetraaceticdianhydride; 3,3′,4,4′-benzophenone tetracarboxylic dianhydride;3,3′,4,4′-biphenyl tetracarboxylic dianhydride; 4,4′-oxydiphthalicanhydride; 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride;2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride;4,4′-bisphenol A diphthalic anhydride;5-(2,5-dioxytetrahydro)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride; ethylene glycol bis(trimellitic anhydride); hydroquinonediphthalic anhydride; allyl nadic anhydride; 2-octen-1-ylsuccinicanhydride; phthalic anhydride; 1,2,3,6-tetrahydrophthalic anhydride;3,4,5,6-tetrahydrophthalic anhydride; 1,8-naphthalic anhydride; glutaricanhydride; dodecenylsuccinic anhydride; hexadecenylsuccinic anhydride;hexahydrophthalic anhydride; methylhexahydrophthalic anhydride;tetradecenylsuccinic anhydride;

wherein X is selected from the group consisting of a saturated or anunsaturated straight-chained or branched alkyl polyester, polyamide,polyether, polysiloxane and polyurethane.